Oil-containing rubber compositions and related methods

ABSTRACT

Disclosed herein are rubber compositions comprising bio-oil produced by a recombinant cell. Also disclosed are methods of controlling the variability of fatty acid content in bio-oil containing rubber compositions or tires comprising at least one component incorporating the bio-oil containing rubber composition, and a method of providing a bio-oil-containing tire with a reduced carbon footprint.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Application Serial No.17/322,132 filed May 17, 2021 and assigned U.S. Pat. No. 11,674,020 andan issue date of Jun. 13, 2023, which is a continuation of U.S.Application Serial No. 16/528,576 filed Jul. 13, 2019 and assigned U.S.Pat. No. 11,008,448 and an issue date of May 18, 2021, which is acontinuation of U.S. Application Serial No. 15/539,050, filed Jun. 22,2017, and issued as U.S. Pat. No. 10,370,526 on Aug. 6, 2019, which is aU.S. National Stage of International Application NumberPCT/US2015/064503, filed on Dec. 8, 2015, which application claimspriority to and any other benefit of U.S. Provisional Pat. ApplicationSerial No. 62/095,955, filed Dec. 23, 2014, and entitled “OIL-CONTAININGRUBBER COMPOSITIONS AND RELATED METHODS,” the entire disclosure of eachof which is incorporated by reference herein.

FIELD OF THE DISCLOSURE

The present disclosure relates to rubber compositions comprising bio-oilproduced by a recombinant cell. The disclosure also relates to methodsof controlling the variability of fatty acid content in bio-oilcontaining rubber compositions or tires comprising at least onecomponent incorporating the bio-oil containing rubber composition, and amethod of providing a bio-oil-containing tire with a reduced carbonfootprint.

BACKGROUND

Most rubber compositions that are intended for use in or used in a tirewill incorporate some amount of oil, either processing oil, extender oilfor one or more rubbers, or both. For many decades the oils utilized insuch rubber compositions were primarily petroleum or fossil-fuel based.However, more recently bio-oils sourced from the components of variousplants have been used in such rubber compositions.

SUMMARY

The present disclosure relates to rubber compositions comprising bio-oilproduced by a recombinant cell. The disclosure also relates to methodsof controlling the variability of fatty acid content in bio-oilcontaining rubber compositions or tires comprising at least onecomponent incorporating the bio-oil containing rubber composition, andto a method of providing a bio-oil-containing tire with a reduced carbonfootprint.

In a first embodiment, a method is disclosed for controlling thevariability of fatty acid content in a bio-oil-containing rubbercomposition. The method comprises incorporating about 5 to about 100 phrof bio-oil produced by a recombinant cell with at least one rubber, atleast one reinforcing filler, and a cure package, thereby forming abio-oil-containing rubber composition.

In a second embodiment, a method is disclosed for providing abio-oil-containing tire with a reduced carbon footprint. The methodcomprises incorporating about 5 to about 100 phr of bio-oil produced bya recombinant cell into at least one rubber, at least one reinforcingfiller, and a cure package, thereby forming an oil-containing rubbercomposition, and incorporating the oil-containing rubber compositioninto at least one component of a tire, thereby producing a reducedcarbon footprint oil containing tire.

In a third embodiment, a bio-oil-containing rubber composition isdisclosed. The composition comprises about 5 to about 100 phr of bio-oilproduced by a recombinant cell, at least one rubber, at least onereinforcing filler, and a cure package.

DETAILED DESCRIPTION

The present disclosure relates to rubber compositions comprising bio-oilproduced by a recombinant cell. The disclosure also relates to methodsof controlling the variability of fatty acid content in bio-oilcontaining rubber compositions or tires comprising at least onecomponent incorporating the bio-oil containing rubber composition, andto a method of providing a bio-oil-containing tire with a reduced carbonfootprint.

In a first embodiment, a method is disclosed for controlling thevariability of fatty acid content in a bio-oil-containing rubbercomposition. The method comprises incorporating about 5 to about 100 phrof bio-oil produced by a recombinant cell with at least one rubber, atleast one reinforcing filler, and a cure package, thereby forming abio-oil-containing rubber composition.

In a second embodiment, a method is disclosed for providing abio-oil-containing tire with a reduced carbon footprint. The methodcomprises incorporating about 5 to about 100 phr of bio-oil produced bya recombinant cell into at least one rubber, at least one reinforcingfiller, and a cure package, thereby forming an oil-containing rubbercomposition, and incorporating the oil-containing rubber compositioninto at least one component of a tire, thereby producing a reducedcarbon footprint oil containing tire.

In a third embodiment, a bio-oil-containing rubber composition isdisclosed. The composition comprises about 5 to about 100 phr of bio-oilproduced by a recombinant cell, at least one rubber, at least onereinforcing filler, and a cure package.

Definitions

The terminology as set forth herein is for description of theembodiments only and should not be construed as limiting the inventionas a whole.

As used herein, the term “majority” means at least 51% by weight.

As used herein, the term “minority” means less than 50% by weight.

As used herein, the term “phr” means the parts by weight of rubber. Ifthe rubber composition comprises more than one rubber, “phr” means theparts by weight per hundred parts of the sum of all rubbers.

As used herein, the term “polybutadiene” is used to indicate a polymerthat is manufactured from cis-1,3-butadiene monomers. The termpolybutadiene is also used interchangeably with the phrase“polybutadiene rubber” and the abbreviation “BR.”

As used herein, the term “polyisoprene” means synthetic polyisoprene. Inother words, the term is used to indicate a polymer that is manufacturedfrom isoprene monomers, and should not be construed as includingnaturally occurring natural rubber (e.g., Hevea natural rubber,guayule-sourced natural rubber or dandelion-sourced natural rubber). Theterm polyisoprene is also used interchangeably with the phrase“polyisoprene rubber” and the abbreviation “IR.”

As used herein, the term “styrene-butadiene rubber” or “SBR” means acopolymer manufactured from styrene and cis-1,3-butadiene monomers.

As used herein, the term “natural rubber” or “NR” means naturallyoccurring rubber such as can be harvested from sources such as Hevearubber trees, and non-Hevea source (e.g., guayule shrubs, and dandelions(e.g., TKS)). In other words, the term “natural rubber” should not beconstrued as including polyisoprene.

For the purpose of this disclosure, any reference to a percent amount ofa component in the rubber composition means a percent by weight, unlessotherwise specified. Similarly, any reference to ratios of componentamounts in the rubber composition means the ratios by weight, unlessotherwise specified. Unless stated to the contrary, discussions hereinrelating to the components and amounts of the rubber compositions of thepresent disclosure should be understood to apply equally to the otherembodiments, e.g., the related methods and the tires (and tire treads)containing the rubber compositions disclosed herein.

Bio-Oil Produced By a Recombinant Cell

As discussed above, according to the first-third embodiments disclosedherein, the rubber composition comprises a bio-oil produced by arecombinant cell. In certain embodiments, the recombinant cell comprisesan algal cell. The use of bio-oil produced by a recombinant cell offersan alternative to traditional bio-oils which are extracted from plants(e.g., sunflower seeds, coconut, soybeans, etc.). Bio-oils produced byrecombinant cells can be produced using a select strain of algal cellswhich are fed with a supply of sugars (e.g., sucrose) and then allowedto ferment and produce a bio-oil with a selected profile. Aftersufficient growth or fermentation has taken place, the bio-oil isisolated from the cells and collected. Exemplary bio-oils produced by arecombinant cell are available from Solazyme, Inc. (South San Francisco,California). Exemplary methods for producing bio-oils produced by arecombinant cell are disclosed in U.S. Pat. Nos. 7,935,515; 8,187,860;8,278,090; 8,476,059; 8,512,999; 8,518,689; 8,580,540; 8,592,188;8,633,012; 8,697,427; 8,765,424; 8,822,177; 8,822,176; 8,846,375; and8,889,401, each of which is incorporated by reference herein.

In certain embodiments, the bio-oil produced by a recombinant cellcomprises an oil having an oleic acid content of at least about 70% anda linoleic acid content of at least about 5%; including an oleic acidcontent of at least 70% and a linoleic acid content of at least 5%; anoleic acid content of at least about 75% and a linoleic acid content ofat least about 6%, an oleic acid content of at least 75% and a linoleicacid content of at least 6%; an oleic acid content of at least about 80%and a linoleic acid content of at least about 7%, and an oleic acidcontent of at least 80% and a linoleic acid content of at least 7%.

In certain embodiments, the bio-oil produced by a recombinant cellcomprises an oil having either at least 50% of its carbons as naphtheniccarbons or at least 50% of its carbons as paraffinic carbons. Standardmethods exist for determining the type of carbon content (i.e.,aromatic, paraffinic or naphthenic), including, but not limited to, ASTMD2140-08. In certain embodiments, the bio-oil produced by a recombinantcell comprises an oil having about 50 to about 70% naphthenic carbons,including 50 to 70%, about 50 to about 60%, and 50 to 60% naphtheniccarbons. In certain embodiments, the bio-oil produced by a recombinantcell comprises an oil having about 60 to about 75% paraffinic carbons,including 60 to 75%, about 65 to about 70%, and 65 to 70% paraffiniccarbons.

In certain embodiments, the bio-oil produced by a recombinant cellcomprises an oil having an oleic acid content of at least about 55%, alinoleic acid content of at least about 15%, and an alpha-linoleic acidcontent of at least about 5%; including an oleic acid content of atleast 55%, a linoleic acid content of at least 15%, and analpha-linoleic acid content of at least 5%; an oleic acid content of atleast about 65%, a linoleic acid content of at least about 20%, and analpha-linoleic acid content of at least about 8%; and an oleic acidcontent of at least 65%, a linoleic acid content of at least 20%, and analpha-linoleic acid content of at least 8%. In certain embodiments, thebio-oil produced by a recombinant cell comprises an oil having an oleicacid content of about 55% to about 90% and an alpha-linoleic acidcontent of about 5% to about 15%; including 55% to 90% oleic acid and analpha-linoleic acid content of 5% to 15%; about 60% to about 85% oleicacid and an alpha-linoleic acid content of about 5% to about 15%; 60% to85% oleic acid and an alpha-linoleic acid content of 5% to 15%; about65% to about 85% oleic acid and an alpha-linoleic acid content of about8% to about 15%; and 65% to 85% oleic acid and an alpha-linoleic acidcontent of 8% to 15%.

In certain embodiments, the bio-oil produced by a recombinant cellcomprises an oil having a lauric acid content of at least about 40%, amyristic acid content of at least about 10%, and a palmitic acid contentof at least about 5%; including a lauric acid content of at least 40%, amyristic acid content of at least 10%, and a palmitic acid content of atleast 5%; including a lauric acid content of at least about 45%, amyristic acid content of at least about 15%, and a palmitic acid contentof at least about 8%; including a lauric acid content of at least 45%, amyristic acid content of at least 15%, and a palmitic acid content of atleast 8%. In certain embodiments, the bio-oil produced by a recombinantcell comprises an oil having a lauric acid content of about 40% to about55%, a myristic acid content of about 10% to about 25%, and a palmiticacid content of about 5% to about 15%; including a lauric acid contentof 40% to 55%, a myristic acid content of 10% to 25%, and a palmiticacid content of 5% to 15%; a lauric acid content of about 45% to about55%, a myristic acid content of about 15% to about 25%, and a palmiticacid content of about 8% to about 15%; and a lauric acid content of 45%to 55%, a myristic acid content of 15% to 25%, and a palmitic acidcontent of 8% to 15%

In certain embodiments, the bio-oil produced by a recombinant cellcomprises an oil having a palmitic acid content of at least about 40%,an oleic acid content of at least about 30%, and a linoleic acid contentof at least about 5%; including a palmitic acid content of at least 40%,an oleic acid content of at least 30%, and a linoleic acid content of atleast 5%; a palmitic acid content of at least about 45%, an oleic acidcontent of at least about 35%, and a linoleic acid content of at leastabout 8%; and a palmitic acid content of at least 45%, an oleic acidcontent of at least 35%, and a linoleic acid content of at least 8%. Incertain embodiments, the bio-oil produced by a recombinant cellcomprises an oil having a palmitic acid content of about 40% to about55%, an oleic acid content of about 30% to about 50%, and a linoleicacid content of about 5% to about 15%; including a palmitic acid contentof 40% to 55%, an oleic acid content of 30% to 50%, and a linoleic acidcontent of 5% to 15%; a palmitic acid content of about 45% to about 55%,an oleic acid content of about 35% to about 45%, and a linoleic acidcontent of about 8% to about 15%; and a palmitic acid content of 45% to55%, an oleic acid content of 35% to 45%, and a linoleic acid content of8% to 15%.

In certain embodiments, the bio-oil produced by a recombinant cellcomprises an oil having an oleic acid content of at least about 15%, alinoleic acid content of at least about 45%, an alpha-linoleic acidcontent of at least about 3%, and a palmitic acid content of at leastabout 5%; including an oleic acid content of at least 15%, a linoleicacid content of at least 45%, an alpha-linoleic acid content of at least3%, and a palmitic acid content of at least 5%; an oleic acid content ofat least about 20%, a linoleic acid content of at least about 50%, analpha-linoleic acid content of at least about 5%, and a palmitic acidcontent of at least about 9%; and an oleic acid content of at least 20%,a linoleic acid content of at least 50%, an alpha-linoleic acid contentof at least 5%, and a palmitic acid content of at least 9%. In certainembodiments, the bio-oil produced by a recombinant cell comprises an oilhaving an oleic acid content of about 15% to about 30%, a linoleic acidcontent of about 45% to about 65%, an alpha-linoleic acid content ofabout 3% to about 15%, and a palmitic acid content of about 5% to about20%; including an oleic acid content of 15% to 30%, a linoleic acidcontent of 45% to 65%, an alpha-linoleic acid content of 3% to 15%, anda palmitic acid content of 5% to 20%; an oleic acid content of about 20%to about 30%, a linoleic acid content of about 45% to about 65%, analpha-linoleic acid content of about 5% to about 12%, and a palmiticacid content of about 9% to about 15%; and an oleic acid content of 20%to 30%, a linoleic acid content of 45% to 65%, an alpha-linoleic acidcontent of 5% to 12%, and a palmitic acid content of 9% to 15%.

In certain embodiments, the bio-oil produced by a recombinant cellcomprises an oil having a linoleic acid content of at least about 60%and an oleic acid content of at least about 8%; including a linoleicacid content of at least 60% and an oleic acid content of at least 8%; alinoleic acid content of at least about 65% and an oleic acid content ofat least about 10%; and a linoleic acid content of at least 65% and anoleic acid content of at least 10%. In certain embodiments, the bio-oilproduced by a recombinant cell comprises an oil having a linoleic acidof about 60% to about 85% linoleic acid and about 8% to about 20% oleicacid; including 60% to 85% linoleic acid and 8% to 20% oleic acid; about65% to about 85% linoleic acid and about 10% to about 20% oleic acid;including 60% to 85% linoleic acid and 8% to 20% oleic acid; and 65% to85% linoleic acid and 10% to 20% oleic acid.

As discussed above, according to the first-third embodiments disclosedherein, the rubber composition comprises about 1 to about 200 phr ofbio-oil produced by a recombinant cell. It should be understood that incertain such embodiments, the rubber composition comprises one bio-oilproduced by a recombinant cell and in other embodiments more than onebio-oil produced by a recombinant cell (i.e., two, three, or more), andthat the amounts referred to herein refer to total amounts of allbio-oil produced by a recombinant cell. In certain embodiments of thefirst-third embodiments, the rubber composition comprises about 5 toabout 100 phr of bio-oil produced by a recombinant cell, including 5 to100 phr, about 5 to about 90 phr, 5 to 90 phr, about 5 to about 80 phr,5 to 80 phr, about 5 to about 70 phr, 5 to 70 phr, about 5 to about 60phr, 5 to 60 phr, about 5 to about 50 phr, 5 to 50 phr, about 5 to about40 phr, 5 to 40 phr, about 10 to about 100 phr, 10 to 100 phr, about 20to about 100 phr, 20 to 100 phr, about 30 to about 100 phr, 30 to 100phr, about 40 to about 100 phr, and 40 to 100 phr.

Rubbers

As discussed above, according to the first-third embodiments disclosedherein, the rubber composition comprises at least one rubber. Theserubber compositions can be understood as comprising 100 parts of rubber(100 phr), which includes at least one rubber. The at least one rubbercan be selected from natural rubber, synthetic rubber, or combinationsthereof. Suitable rubbers for use in the rubber composition are wellknown to those skilled in the art and include, but are not limited tothe following: synthetic polyisoprene rubber, natural rubber,styrene-butadiene rubber (SBR), styrene-isoprene rubber,butadiene-isoprene-rubber, styrene-isoprene-butadiene rubber,polybutadiene, butyl rubber (both halogenated and non-halogenated),neoprene (polychloroprene), ethylene-propylene rubber,ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber(NBR), silicone rubber, fluorinated rubber, polyacrylate rubber(copolymer of acrylate monomer and vinyl ether), ethylene acrylicrubber, ethylene vinyl acetate copolymer (EVA), epichlorohydrin rubbers,chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers,nitrile rubber, halogenated nitrile rubber, hydrogenated nitrile rubber,and tetrafluoroethylene-propylene rubber, and combinations thereof.Examples of fluorinated rubber include perfluoroelastomer rubber,fluoroelastomer, fluorosilicone, and tetrafluoroethylene-propylenerubber.

In certain embodiments of the first-third embodiments disclosed herein,at least a majority (by weight) of the at least one rubber comprises atleast one of: natural rubber, polyisoprene rubber, polybutadiene rubber,and styrene-butadiene rubber; in such embodiments, one or more than onetype of any of the foregoing rubbers can be utilized. In certainembodiments, at least 60% by weight (at least 60 phr), at least 70% byweight (at least 70 phr), at least 80% by weight (at least 80 phr), atleast 90% by weight (at least 90 phr), at least 95% by weight (at least95 phr), or even 100% by weight (100 phr) of the rubber comprises atleast one of: natural rubber, synthetic polyisoprene rubber,polybutadiene rubber, and styrene-butadiene rubber.

In certain embodiments of the first-third embodiments disclosed herein,a minority (by weight) of the at least one rubber comprises at least oneof: styrene-isoprene rubber, butadiene-isoprene-rubber,styrene-isoprene-butadiene rubber, butyl rubber (both halogenated andnon-halogenated), neoprene (polychloroprene), ethylene-propylene rubber,ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber(NBR), silicone rubber, fluorinated rubber, polyacrylate rubber(copolymer of acrylate monomer and vinyl ether), ethylene acrylicrubber, ethylene vinyl acetate copolymer (EVA), epichlorohydrin rubbers,chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers,nitrile rubber, halogenated nitrile rubber, hydrogenated nitrile rubber,and tetrafluoroethylene-propylene rubber. In certain embodiments, up to40% by weight (up to 40 phr), up to 30% by weight (up to 30 phr), up to20% by weight (up to 20 phr), up to 10% by weight (up to 10 phr), up to5% by weight (up to 5 phr) of the rubber comprises at least one of:styrene-isoprene rubber, butadiene-isoprene-rubber,styrene-isoprene-butadiene rubber, butyl rubber (both halogenated andnon-halogenated), neoprene (polychloroprene), ethylene-propylene rubber,ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber(NBR), silicone rubber, fluorinated rubber, polyacrylate rubber(copolymer of acrylate monomer and vinyl ether), ethylene acrylicrubber, ethylene vinyl acetate copolymer (EVA), epichlorohydrin rubbers,chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers,nitrile rubber, halogenated nitrile rubber, hydrogenated nitrile rubber,and tetrafluoroethylene-propylene rubber. In other embodiments, 0% byweight (0 phr) of the rubber comprises styrene-isoprene rubber,butadiene-isoprene-rubber, styrene-isoprene-butadiene rubber, butylrubber (both halogenated and non-halogenated), neoprene(polychloroprene), ethylene-propylene rubber, ethylene-propylene-dienerubber (EPDM), acrylonitrile-butadiene rubber (NBR), silicone rubber,fluorinated rubber, polyacrylate rubber (copolymer of acrylate monomerand vinyl ether), ethylene acrylic rubber, ethylene vinyl acetatecopolymer (EVA), epichlorohydrin rubbers, chlorinated polyethylenerubbers, chlorosulfonated polyethylene rubbers, nitrile rubber,halogenated nitrile rubber, hydrogenated nitrile rubber, andtetrafluoroethylene-propylene rubber; in certain such embodiments, 100phr of the rubber comprises at least one of: natural rubber, syntheticpolyisoprene rubber, polybutadiene rubber, and styrene-butadiene rubber.In yet other embodiments, up to 100% by weight (100 phr), including upto 90% by weight (90 phr), up to 80% by weight (80 phr), up to 70% byweight (70 phr) and up to 60% by weight (60 phr) of the rubber comprisesat least one of: styrene-isoprene rubber, butadiene-isoprene-rubber,styrene-isoprene-butadiene rubber, butyl rubber (both halogenated andnon-halogenated), neoprene (polychloroprene), ethylene-propylene rubber,ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber(NBR), silicone rubber, fluorinated rubber, polyacrylate rubber(copolymer of acrylate monomer and vinyl ether), ethylene acrylicrubber, ethylene vinyl acetate copolymer (EVA), epichlorohydrin rubbers,chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers,nitrile rubber, halogenated nitrile rubber, hydrogenated nitrile rubber,and tetrafluoroethylene-propylene rubber.

In certain embodiments of the first-third embodiments disclosed herein,the at least one rubber comprises a polymer, a copolymer, or acombination thereof (i.e., more than one polymer, more than onecopolymer, one polymer and one copolymer, more than one polymer and onecopolymer, more than one copolymer and one polymer, or more than onecopolymer and more than one polymer) when more than one rubber isutilized. In certain embodiments of the first-third embodimentsdisclosed herein, the at least one rubber includes at least one dienemonomer-containing polymer or copolymer. Examples of suitable dienemonomers according to certain embodiments of the first-third embodimentsdisclosed herein include, but are not limited to, 1,3-butadiene,isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene,1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene, andderivatives thereof. It should be understood that mixtures of two ormore dienes may be utilized in certain embodiments. Non-limitingexamples of suitable polymers that are diene monomer-containing polymersor copolymers include, but are not limited to, styrene-butadiene rubber,polybutadiene, polyisoprene, styrene-isoprene rubber,styrene-butadiene-isoprene rubber, and natural rubber. In certainembodiments of the first-third embodiments disclosed herein, the atleast one rubber is at least one of: styrene-butadiene rubber,polybutadiene, synthetic polyisoprene rubber, and natural rubber.

As discussed above, in certain embodiments according to the first-thirdembodiments, the at least one rubber comprises polybutadiene. In certainembodiments according to the first-third embodiments, the polybutadienecomprises a high cis polybutadiene. In certain embodiments according tothe first-third embodiments, the high cis polybutadiene has a cis1,4-bond content of 85% of greater, 90% or greater, 92% or greater, or95% or greater. In certain embodiments of the first-third embodiments,the polybutadiene has a cis 1,4-bond content of 85-99%, 90-99%, 90-98%,90-97%, 92-99%, 92-98%, 92-97%, 95-99%, 95-98%, or 95-97%. In certainembodiments according to the first-third embodiments, the polybutadienecomprises a low cis polybutadiene. In certain embodiments according tothe first-third embodiments, the polybutadiene comprises a low cispolybutadiene. In certain embodiments according to the first-thirdembodiments, the low polybutadiene has a cis 1,4- bond content of lessthan 50%, less than 45%, or less than 40%.

Generally, various polymerization methods are known for producingpolybutadiene having a cis 1,4-bond content of 85% or greater, 90% orgreater, 92% or greater, or 95% or greater and it should be understoodthat the particular method by which the polybutadiene is produced is notlimited as long as the resulting polybutadiene has the specified cis1,4-bond content. The percentages are based upon the number of diene merunits adopting the cis-1,4 linkage versus the total number of diene merunits. Polymerization of high-cis 1,4-polybutadiene is described in U.S.Pat. Nos. 3,297,667, 3,541,063, 3,794,604, 4,461,883, 4,444,903,4,525,594, 4,699,960, 5,017,539, 5,428,119, 5,064,910, and 5,844,050,7,094,849, all of which are hereby incorporated by reference. Exemplarypolymerization methods include, but are not limited to, those employingZiegler-Natta catalysts based on transition metals (e.g., lanthanidessuch as neodymium), nickel catalysts and titanium-based catalysts aswell as solution, emulsion and bulk polymerization processes. Generally,the cis 1,4-, vinyl 1,2-, and trans 1,4- bond linkage contents in agiven polymer such as polybutadiene can be determined by standard andwell-established analytical methods such as infrared spectroscopy.

As discussed above, in certain embodiments according to the first-thirdembodiments, the at least one rubber comprises polyisoprene. In certainembodiments according to the first-third embodiments, the polyisoprenecomprises high cis polyisoprene. In certain embodiments according to thefirst-third embodiments, the high cis polyisoprene has a cis 1,4-bondcontent of 90% of greater. In certain embodiments of the first-thirdembodiments, the polyisoprene has a cis 1,4-bond content of 90% orgreater, 92% or greater, or 95% or greater. In certain embodiments ofthe first-third embodiments, the polyisoprene has a cis 1,4-bond contentof 90-99%, 90-98%, 90-97%, 92-99%, 92-98%, 92-97%, 95-99%, 95-98%, or95-97%.

Generally, various polymerization methods are known for producingpolyisoprene, including polyisoprene having a cis 1,4-bond content of90% or greater, and it should be understood that the particular methodby which the polyisoprene is produced is not limited as long as theresulting polymer has the desired cis 1,4-bond content. As previouslydiscussed with respect to polybutadiene, the percentages are based uponthe number of diene mer units adopting the cis-1,4 linkage versus thetotal number of diene mer units. Polymerization of high-cis polyisopreneis described in U.S. Pat. Nos. 8,664,343; 8,188,201; 7,008,899;6,897,270; and 6,699,813, all of which are hereby incorporated byreference. Exemplary polymerization methods include, but are not limitedto, those employing Ziegler-Natta catalyst systems and those employinganionic polymerization with organometallic catalysts such as alkyllithium in hydrocarbon solvents. As previously discussed with respect topolybutadiene, the cis-1,4-, cis-1,2-, and trans-1,4-linkage contents ina given polymer such as polyisoprene can be determined by standard andwell-established analytical methods such as infrared spectroscopy.

As discussed above, in certain embodiments according to the first-thirdembodiments, the at least one rubber comprises the copolymerstyrene-butadiene rubber (SBR). SBR is a copolymer of styrene andbutadiene monomers. In certain embodiments according to the first-thirdembodiments disclosed herein, the SBR used in the rubber compositioncomprises about 10 to about 50% styrene monomer and about 50 to about90% butadiene monomer by weight. In certain embodiments according to thefirst-third embodiments disclosed herein, the SBR used in the rubbercomposition comprises 10 to 50% styrene monomer and 50 to 90% butadienemonomer by weight. Generally, SBR is produced by solution or emulsionpolymerization methods; however, it should be understood that theparticular method by which the SBR is produced is not limited. Thestyrene and butadiene monomer content in a given SBR copolymer can bedetermined by standard and well-established analytical methods such asinfrared spectroscopy.

Numerous commercial sources of the foregoing rubbers are well-known. Asnon-limiting examples, Firestone Polymers offers various grades of itsDiene™ polybutadiene which have varying cis 1,4-bond contents (e.g., 40%and 96%) as well as various grades of its Duradene™ solution polymerizedstyrene-butadiene copolymer. Other commercial sources of the rubbers arewell known, including sources for emulsion polymerized styrene-butadienecopolymer, functionalized versions of styrene-butadiene copolymer,neoprene, polybutadiene, synthetic polyisoprene rubber, and naturalrubber.

In certain embodiments according to the first-third embodimentsdisclosed herein, the at least one rubber of the rubber compositioncomprises a functionalized polymer. In certain such embodiments, therubber composition comprises about 5 to about 100 phr of at least onefunctionalized polymer, including 5 phr to 100 phr, about 10 to about 90phr, 10 phr to 90 phr, about 10 to about 70 phr, 10 phr to 70 phr, about10 to about 50 phr, and 10 phr to 50 phr. In certain embodimentsaccording to the first-third embodiments disclosed herein, thefunctionalized polymer comprises a polymer with a silica-reactivefunctional group, a nitrogen-containing functional group, anoxygen-containing functional group, a sulfur-containing functionalgroup, or a combination of the foregoing. Non-limiting examples ofsilica-reactive functional groups that are known to be utilized infunctionalizing conjugated diene polymers and are suitable for use inthe rubber compositions of certain embodiments of the first-thirdembodiments disclosed herein include nitrogen-containing functionalgroups, silicon-containing functional groups, oxygen orsulfur-containing functional groups, and metal-containing functionalgroups. As used herein, the term functionalized polymer should beunderstood to include polymers (including conjugated dienemonomer-containing polymer or copolymer rubbers) with a functional groupat one or both terminus (e.g., from use of a functionalized initiator, afunctionalized terminator, or both), a functional group in the mainchain of the polymer, and combinations thereof. For example, asilica-reactive functionalized polymer may have the functional group atone or both terminus, in the main chain thereof, or both in the mainchain and at one or both terminus.

Non-limiting examples of nitrogen-containing functional groups that areknown to be utilized in functionalizing rubbers include, but are notlimited to, any of a substituted or unsubstituted amino group, an amideresidue, an isocyanate group, an imidazolyl group, an indolyl group, anitrile group, a pyridyl group, and a ketimine group. The foregoingsubstituted or unsubstituted amino group should be understood to includea primary alkylamine, a secondary alkylamine, or a cyclic amine, and anamino group derived from a substituted or unsubstituted imine. Incertain embodiments according to the first-third embodiments disclosedherein, the rubber composition comprises a functionalized conjugateddiene monomer-containing polymer or copolymer rubber having at least onefunctional group selected from the foregoing list.

Non-limiting examples of silicon-containing functional groups that areknown to be utilized in functionalizing rubbers include, but are notlimited to, an organic silyl or siloxy group, and more precisely, thefunctional group may be selected from an alkoxysilyl group, analkylhalosilyl group, a siloxy group, an alkylaminosilyl group, and analkoxyhalosilyl group. Suitable silicon-containing functional groups foruse in functionalizing rubbers also include those disclosed in U.S. Pat.No. 6,369,167, the entire disclosure of which is hereby incorporated byreference. In certain embodiments according to the first-thirdembodiments disclosed herein, the rubber composition comprises afunctionalized rubber having at least one functional group selected fromthe foregoing list.

Non-limiting examples of oxygen or sulfur-containing functional groupsthat are known to be utilized in functionalizing rubbers include, butare not limited to, a hydroxyl group, a carboxyl group, an epoxy group,a glycidoxy group, a diglycidylamino group, a cyclic dithiane-derivedfunctional group, an ester group, an aldehyde group, an alkoxy group, aketone group, a thiocarboxyl group, a thioepoxy group, a thioglycidoxygroup, a thiodiglycidylamino group, a thioester group, a thioaldehydegroup, a thioalkoxy group and a thioketone group. In certainembodiments, the foregoing alkoxy group may be an alcohol-derived alkoxygroup derived from a benzophenone. In certain embodiments according tothe first-third embodiments disclosed herein, the rubber compositioncomprises a functionalized diene monomer-containing polymer or copolymerrubber having at least one functional group selected from the foregoinglist.

Generally, rubbers, including diene monomer-containing polymer orcopolymer rubbers, may be prepared and recovered according to varioussuitable methods such as batch, semi-continuous, or continuousoperations, as are well known to those having skill in the art. Thepolymerization can also be carried out in a number of differentpolymerization reactor systems, including but not limited to bulkpolymerization, vapor phase polymerization, solution polymerization,suspension polymerization, coordination polymerization, and emulsionpolymerization. The polymerization may be carried out using a freeradical mechanism, an anionic mechanism, a cationic mechanism, or acoordination mechanism. All of the above polymerization methods are wellknown to persons skilled in the art. However, for exemplary purposes, ashort description of polymerization via an anionic mechanism is given.

When rubbers, such as diene monomer-containing polymer or copolymerrubbers, are produced through anionic polymerization, an organicalkaline metal compound, preferably a lithium-containing compound, istypically used as a polymerization initiator. Examples oflithium-containing compounds used as polymerization initiators include,but are not limited to, hydrocarbyl lithium compounds, lithium amidecompounds, and similar lithium compounds. The amount of the lithiumcompound used as the polymerization initiator is preferably within arange of 0.2 to 20 millimoles per 100 g of the monomer.

Non-limiting examples of hydrocarbyl lithium compounds include ethyllithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyllithium, tert-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyllithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyllithium, cyclopentyl lithium, a reaction product of diisopropenylbenzeneand butyl lithium, and mixtures thereof. Among these, alkyl lithiumcompounds such as ethyl lithium, n-propyl lithium, isopropyl lithium,n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl lithiumand so on are preferable, and n-butyl lithium is particularlypreferable.

Methods for producing rubbers, such as diene-monomer-containing polymeror copolymer rubbers, through anionic polymerization using an organicalkaline metal compound as the polymerization initiator are notparticularly limited. For example, a diene monomer-containing polymer orcopolymer rubber can be produced by polymerizing a conjugated dienemonomer alone or a mixture of a diene monomer and aromatic vinylcompound in a hydrocarbon solvent inactive to the polymerizationreaction. Non-limiting examples of the hydrocarbon solvent inactive tothe polymerization reaction include propane, n-butane, isobutane,n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene,isobutene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene,2-hexene, benzene, toluene, xylene, ethylbenzene and mixtures thereof.

The anionic polymerization may be carried out in the presence of arandomizer. The randomizer can control the microstructure of the dienecompound, and has an action that the 1,2-bond content in butadiene unitof the polymer using, for example, butadiene as a monomer is controlled,and butadiene unit and styrene unit in the copolymer using butadiene andstyrene as a monomer are randomized, or the like. Non-limiting examplesof the randomizer include dimethoxybenzene, tetrahydrofuran,dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycoldimethyl ether, bis tetrahydrofuryl propane, triethylamine, pyridine,N-methylmorpholine, N,N,N′N′-tetramethyl ethylenediamine,1,2-dipiperidinoethane, potassium-t-amylate, potassium-t-butoxide,sodium-t-amylate and so on. The amount of the randomizer used ispreferably within a range of 0.01 to 100 molar equivalents per 1 mol ofthe organic alkaline metal compound as a polymerization initiator.

The anionic polymerization may be carried out through any of solutionpolymerization, vapor phase polymerization and bulk polymerization. Inthe solution polymerization, the concentration of the monomer in thesolution is preferably within a range of 5 to 50% by mass, morepreferably 10 to 30% by mass. When the conjugated diene monomer and avinyl aromatic monomer are used together, the content of the vinylaromatic monomer in the mixture is preferably within a range of 3 to 50%by mass, more preferably 4 to 45% by mass. Also, the polymerizationsystem is not particularly limited and may be a batch system or acontinuous system.

The polymerization temperature in the anionic polymerization ispreferably within a range of 0 to 150° C., more preferably 20 to 130° C.The polymerization may be carried out under a generating pressure or,preferably, at a pressure sufficient to keep the reaction monomerssubstantially in a liquid phase. When the polymerization reaction iscarried out under a pressure higher than the generating pressure, thereaction system is preferably pressurized with an inert gas. Preferably,any reaction-obstructing substances, such as water, oxygen, carbondioxide, protonic compounds, and the like are removed before beginningthe polymerization reaction.

Typically, in the rubber compositions according to the first-thirdembodiments disclosed herein, the overall composition contains 100 phr(in total) of at least one rubber. In other words, the total amount ofall rubbers is considered to be 100 parts (by weight) and denoted 100phr. Other components are added based upon 100 parts (in total) ofrubber(s). As a non-limiting example, 60 parts of styrene-butadienecopolymer could be utilized along with 40 parts of polybutadiene polymerand 60 parts of silica; these amounts would be described herein as 60phr of styrene-butadiene copolymer, 40 phr of polybutadiene polymer and60 phr of silica.

Oil-Extended Rubbers

Also disclosed herein, is an oil-extended rubber comprising at least onerubber and about 5 to about 50 phr (including 5 to 50 phr) of a bio-oilproduced by a recombinant cell. In certain embodiment of the foregoing,the oil-extended rubber comprises about 5 to about 45 phr of a bio-oilproduced by a recombinant cell, including 5 to 45 phr, about 5 to about40 phr, and 5 to 40 phr. The rubber in the oil-extended rubber maycomprise any of the rubber discussed above. In certain embodiments, theat least one rubber of the oil-extended rubber comprises at least onediene monomer-containing polymer or copolymer; in certain suchembodiments, the at least one diene-monomer-containing polymer orcopolymer comprises at least one of polybutadiene, styrene-butadienecopolymer, natural rubber, or polyisoprene.

Reinforcing Filler(s)

As discussed above, according to the first-third embodiments disclosedherein, the rubber composition comprises about 5 to about 200 phr of atleast one reinforcing filler. One or more than one reinforcing fillermay be utilized in the rubber compositions according to the first-thirdembodiments disclosed herein. In certain embodiments of the first-thirdembodiments disclosed herein, the total amount of the reinforcing filleris 5 to 200 phr, including about 10 to about 200 phr, 10 to 200 phr,about 10 to about 175 phr, 10 to 175 phr, about 25 to about 150 phr, 25to 150 phr, about 35 to about 150 phr, 35 to 150 phr, about 25 to about125 phr, 25 to 125 phr, about 25 to about 100 phr, 25 to 100 phr, about25 to about 80 phr, 25 to 80 phr, about 35 to about 125 phr, 35 to 125phr, about 35 to about 100 phr, 35 to 100 phr, about 35 to about 80 phr,and 35 to 80 phr of at least one reinforcing filler. In certainembodiments, the useful upper range for the amount of reinforcing fillercan be considered to be somewhat limited by the high viscosity impartedby fillers of this type.

As used herein, the term “reinforcing” with respect to “reinforcingcarbon black filler,” “reinforcing silica filler,” and “reinforcingfillers” generally should be understood to encompass both fillers thatare traditionally described as reinforcing as well as fillers that maytraditionally be described as semi-reinforcing. Traditionally, the term“reinforcing filler” is used to refer to a particulate material that hasa nitrogen absorption specific surface area (N₂SA) of more than about100 m²/g, and in certain instances more than 100 m²/g, more than about125 m²/g, more than 125 m²/g, or even more than about 150 m²/g or morethan 150 m²/g. Alternatively, the traditional use of the term“reinforcing filler” can also be used to refer to a particulate materialthat has a particle size of about 10 nm to about 50 nm (including 10 nmto 50 nm). Traditionally, the term “semi-reinforcing filler” is used torefer to a filler that is intermediary in either particle size, surfacearea (N₂SA), or both, to a non-reinforcing filler and a reinforcingfiller. In certain embodiments of the first-third embodiments disclosedherein, the term “reinforcing filler” is used to refer to a particulatematerial that has a nitrogen absorption specific surface area (N₂SA) ofabout 20 m²/g or greater, including 20 m²/g or greater, more than about50 m²/g, more than 50 m²/g, more than about 100 m²/g, more than 100m²/g, more than about 125 m²/g, and more than 125 m²/g. In certainembodiments of the first-third embodiments disclosed herein, the term“reinforcing filler” is used to refer to a particulate material that hasa particle size of about 10 nm up to about 1000 nm, including 10 nm to1000 nm, about 10 nm up to about 50 nm and 10 nm to 50 nm.

In certain embodiments of the first-third embodiments disclosed herein,the at least one reinforcing filler comprises at least one of: carbonblack or silica. In other words, in such embodiments, the at least onereinforcing filler comprises at least one carbon black, at least onesilica, or at least one carbon black and at least one silica. In certainembodiments of the first-third embodiments disclosed herein, the atleast one reinforcing filler comprises at least one of: carbon black orsilica, and further comprises at least one additional reinforcingfiller. In other words, in such embodiments, the at least onereinforcing filler comprises at least one carbon black and at least oneadditional reinforcing filler (other than silica), at least one silicaand at least one additional reinforcing filler (other than carbonblack), or at least one silica and at least one carbon black and atleast one additional reinforcing filler (other than the carbon black orsilica). As discussed in more detail below, in certain embodiments ofthe first-third embodiments disclosed herein, the at least onereinforcing filler comprises at least one reinforcing filler other thancarbon black or silica.

Silica

As discussed above, in certain embodiments of the first-thirdembodiments disclosed herein the rubber composition comprises at leastone reinforcing filler which comprises silica. Suitable reinforcingsilica fillers for use in the rubber composition of certain embodimentsof the first-third embodiments disclosed herein are well known.Non-limiting examples of reinforcing silica fillers suitable for use inthe rubber compositions of certain embodiments of the first-thirdembodiments disclosed herein include, but are not limited to,precipitated amorphous silica, wet silica (hydrated silicic acid), drysilica (anhydrous silicic acid), fumed silica, calcium silicate and thelike. Other suitable reinforcing silica fillers for use in rubbercompositions of certain embodiments of the first-third embodimentsdisclosed herein include, but are not limited to, aluminum silicate,magnesium silicate (Mg₂SiO₄, MgSiO₃ etc.), magnesium calcium silicate(CaMgSiO₄), calcium silicate (Ca₂SiO₄ etc.), aluminum silicate (Al₂SiO₅,Al₄.3SiO₄.5H₂O etc.), aluminum calcium silicate (Al₂O₃.CaO₂SiO₂, etc.),and the like. Among the listed reinforcing silica fillers, precipitatedamorphous wet-process, hydrated silica fillers are preferred. Suchreinforcing silica fillers are produced by a chemical reaction in water,from which they are precipitated as ultrafine, spherical particles, withprimary particles strongly associated into aggregates, which in turncombine less strongly into agglomerates. The surface area, as measuredby the BET method, is a preferred measurement for characterizing thereinforcing character of different reinforcing silica fillers. Incertain embodiments of the first-third embodiments disclosed herein, therubber composition comprises a reinforcing silica filler having asurface area (as measured by the BET method) of about 32 m²/g to about400 m²/g (including 32 m²/g to 400 m²/g), with the range of about 100m²/g to about 300 m²/g (including 100 m²/g to 300 m²/g) being preferred,and the range of about 150 m²/g to about 220 m²/g (including 150 m²/g to220 m²/g) being included. In certain embodiments of the first-thirdembodiments disclosed herein, the rubber composition comprisesreinforcing silica filler having a pH of about 5.5 to about 7 orslightly over 7, preferably about 5.5 to about 6.8. Some of thecommercially available reinforcing silica fillers which can be used inthe rubber compositions of certain embodiments of the first-thirdembodiments disclosed herein include, but are not limited to,Hi-Sil®190, Hi-Sil®210, Hi-Sil®215, Hi-Sil®233, Hi-Sil®243, and thelike, produced by PPG Industries (Pittsburgh, Pa.). As well, a number ofuseful commercial grades of different reinforcing silica fillers arealso available from Degussa Corporation (e.g., VN2, VN3), Rhone Poulenc(e.g., Zeosil™ 1165MP), and J. M. Huber Corporation.

In certain embodiments of the first-third embodiments disclosed herein,as discussed in more detail below, the reinforcing silica fillercomprises a silica that has been pre-treated with a silica couplingagent; preferably the pre-treated silica comprises a silica that hasbeen pre-treated with a silane-containing silica coupling agent.

Carbon Black

As discussed above, in certain embodiments of the first-thirdembodiments disclosed herein the rubber composition comprises at leastone reinforcing filler which comprises silica. As discussed in moredetail below, most carbon blacks are commonly understood to bereinforcing fillers. In certain embodiments of the first-thirdembodiments disclosed herein, the rubber composition comprises carbonblack in an amount of from zero to about 50% by weight of the totalreinforcing filler, including zero to 50%, about 5% to about 30%, 5% to30%, from about 5% to about 20%, 5% to 20%, about 10% to about 30%, 10%to 30%, about 10% to about 20%, and 10% to 20% by weight of the totalreinforcing filler. In certain embodiments of the first-thirdembodiments disclosed herein, the carbon black comprises no more thanabout 30% by weight (including no more than 30% by weight) of the totalreinforcing filler in the rubber composition. In certain embodiments ofthe first-third embodiments disclosed herein, the rubber compositioncomprises about 5 to about 100 phr (including 5 to 100 phr) of one ormore carbon blacks.

Generally, suitable carbon black for use as a reinforcing filler in therubber composition of certain embodiments of the first-third embodimentsdisclosed herein includes any of the commonly available,commercially-produced carbon blacks, including those having a surfacearea of at least about 20 m²/g (including at least 20 m²/g) and, morepreferably, at least about 35 m²/g up to about 200 m²/g or higher(including 35 m²/g up to 200 m²/g). Surface area values used in thisapplication are determined by ASTM D-1765 using thecetyltrimethylammonium bromide (CTAB) technique. Among the useful carbonblacks are furnace black, channel blacks, and lamp blacks. Morespecifically, examples of useful carbon blacks include super abrasionfurnace (SAF) blacks, high abrasion furnace (HAF) blacks, fast extrusionfurnace (FEF) blacks, fine furnace (FF) blacks, intermediate superabrasion furnace (ISAF) blacks, semi-reinforcing furnace (SRF) blacks,medium processing channel blacks, hard processing channel blacks andconducting channel blacks. Other carbon blacks which can be utilizedinclude acetylene blacks. In certain embodiments of the first-thirdembodiments disclosed herein, the rubber composition includes a mixtureof two or more of the foregoing blacks. Typical suitable carbon blacksfor use in certain embodiments of the first-third embodiments disclosedherein are N-110, N-220, N-339, N-330, N-351, N-550, and N-660, asdesignated by ASTM D-1765-82a. The carbon blacks utilized can be inpelletized form or an unpelletized flocculent mass. Preferably, for moreuniform mixing, unpelletized carbon black is preferred.

Other Fillers

As discussed above, in certain embodiments of the first-thirdembodiments disclosed herein, the rubber composition comprises at leastone reinforcing filler comprising a reinforcing filler other than carbonblack or silica. In those embodiments of the first-third embodimentsdisclosed herein where the rubber composition comprises at least onereinforcing filler comprising silica, carbon black, or both, thisreinforcing filler other than carbon black or silica may be referred toas an additional reinforcing filler. In certain embodiments of thefirst-third embodiments disclosed herein, the rubber compositioncomprises at least one of: carbon black or silica, and at least oneadditional reinforcing filler. In other words, in certain embodiments ofthe first-third embodiments disclosed herein, the rubber compositioncomprises at least reinforcing carbon black and at least one additionalreinforcing filler; at least one reinforcing silica filler and at leastone additional reinforcing filler; or at least one reinforcing carbonblack, at least one reinforcing silica filler, and at least oneadditional reinforcing filler.

Suitable reinforcing fillers other than carbon black or silica for usein the rubber composition of certain embodiments of the first-thirdembodiments disclosed herein are well known. Non-limiting examples ofsuitable additional reinforcing fillers for use in the rubbercompositions of certain embodiments of the first-third embodimentsdisclosed herein include, but are not limited to, alumina, aluminumhydroxide, clay (reinforcing grades), magnesium hydroxide, boronnitride, aluminum nitride, titanium dioxide, reinforcing zinc oxide, andcombinations thereof.

As discussed above, in certain embodiments of the first-thirdembodiments disclosed herein, the rubber compositions comprises at leastone non-reinforcing filler. In certain embodiments of the first-thirdembodiments disclosed herein, the rubber composition comprises at leastone non-reinforcing filler in addition to the at least one reinforcingfiller. In other embodiments of the first-third embodiments disclosedherein, the rubber composition comprises at least one non-reinforcingfiller without the need for any reinforcing filler, i.e., in suchembodiments the at least one non-reinforcing filler is essential while areinforcing filler is not.

In certain embodiments of the first-third embodiments, the rubbercomposition further comprises at least one non-reinforcing filler. Incertain embodiments, the term “non-reinforcing filler” is used to referto a particulate material that has a nitrogen absorption specificsurface area (N₂SA) of less than about 20 m²/g (including less than 20m²/g), and in certain embodiments less than about 10 m²/g (includingless than 10 m²/g). The N₂SA surface area of a particulate material canbe determined according to various standard methods including ASTMD6556. In certain embodiments of the compositions and methods disclosedherein, the term “non-reinforcing filler” is used to refer to aparticulate material that has a particle size of greater than about 1000nm (including greater than 1000 nm).

Suitable non-reinforcing fillers for use in the rubber composition ofcertain embodiments of the first-third embodiments disclosed herein arewell known. In certain embodiments of the first-third embodimentsdisclosed herein, the rubber composition further comprises at least oneof the following non-reinforcing fillers: clay, graphite, talc, mica,titanium dioxide, magnesium dioxide, aluminum oxide, titanium oxide,calcium oxide, aluminum hydroxide, starch, boron nitride, siliconnitride, aluminum nitride, etc.), silicon carbide, aluminum carbonate(Al₂(CO₃)₂, non-reinforcing grades of calcium carbonate (CaCO₃),magnesium carbonate (MgCO₃), calcium oxide, mica, calcium oxide, boronnitride, silicon nitride, aluminum nitride, calcium silicate (or siliconcarbide (Ca₂SiO₄, etc.), or crystalline aluminosilicates. In certainembodiments of the first-third embodiments disclosed herein, the rubbercomposition further comprises a non-reinforcing carbon black. Examplesof suitable carbon blacks having a nitrogen surface area of no more than20 m²/g include, but are not limited to, thermal blacks or the N9 seriescarbon blacks (also referred to as the N-900 series), such as those withthe ASTM designation N-907, N-908, N-990, and N-991. Various carbonblacks meeting the foregoing are commercially available, including butnot limited to Thermax® N990 carbon black from Cancarb Limited (MedicineHat, Alberta, Canada).

In certain embodiments of the first-third embodiments, the rubbercomposition further comprises at least one inorganic filler (other thansilica). Such an inorganic filler can be described as a non-silicainorganic filler. In other words, certain embodiments of the first-thirdembodiments disclosed herein, the rubber composition comprises at leastone inorganic filler (other than silica) in addition to the at least onereinforcing filler. In other embodiments of the first-third embodimentsdisclosed herein, the rubber composition comprises at least oneinorganic filler (other than silica) without the need for anyreinforcing filler, i.e., in such embodiments the at least one inorganicfiller (other than silica) is essential while a reinforcing filler isnot.

Inorganic fillers (other than silica) suitable for use in rubbercompositions are well known. In certain embodiments of the first-thirdembodiments disclosed herein, the rubber composition comprises at one ofthe following inorganic fillers: aluminum hydroxide, talc, clay, alumina(Al₂O₃), aluminum hydrate (Al₂O₃H₂O), aluminum hydroxide (Al(OH)₃),aluminum carbonate (Al₂(CO₃)₂), aluminum nitride, aluminum magnesiumoxide (MgOAl₂O₃), aluminum silicate (Al₂SiO₅, A1₄.3SiO₄.5H₂O etc.),aluminum calcium silicate (Al₂O₃.CaO₂SiO₂, etc.), pyrofilite(Al₂O₃4SiO₂.H₂O), bentonite (Al₂O₃.4SiO₂.2H₂O), boron nitride, mica,kaolin, glass balloon, glass beads, calcium oxide (CaO), calciumhydroxide (Ca(OH)₂), calcium carbonate (CaCO₃), calcium silicate(Ca₂SiO₄ etc.), magnesium carbonate, magnesium hydroxide (MH(OH)₂),magnesium oxide (MgO), magnesium carbonate (MgCO₃), magnesium silicate(Mg₂SiO₄, MgSiO₃ etc.), magnesium calcium silicate (CaMgSiO₄), titaniumoxide, titanium dioxide, potassium titanate, barium sulfate, zirconiumoxide (ZrO₂), zirconium hydroxide [Zr(OH)₂.nH₂O], zirconium carbonate[Zr(CO₃)_(2]), crystalline aluminosilicates, reinforcing grades of zincoxide (i.e., reinforcing zinc oxide), and combinations thereof. Incertain embodiments of the first-third embodiments disclosed herein, therubber composition comprises at least one reinforcing filler (asdiscussed above) and at least one of the following inorganic fillers:aluminum hydroxide, talc, clay, alumina (Al₂O₃), aluminum hydrate(Al₂O₃H₂O), aluminum hydroxide (Al(OH)₃), aluminum carbonate(Al₂(CO₃)₂), aluminum nitride, aluminum magnesium oxide (MgOAl₂O₃),aluminum silicate (Al₂SiO₅, Al₄.3SiO₄.5H₂O etc.), aluminum calciumsilicate (A1₂O₃.CaO₂SiO₂, etc.), pyrofilite (A1₂O₃4SiO₂.H₂O), bentonite(A1₂O₃.4SiO₂.2H₂O), boron nitride, mica, kaolin, glass balloon, glassbeads, calcium oxide (CaO), calcium hydroxide (Ca(OH)₂), calciumcarbonate (CaCO₃), calcium silicate (Ca₂SiO₄ etc.), magnesium carbonate,magnesium hydroxide (MH(OH)₂), magnesium oxide (MgO), magnesiumcarbonate (MgCO₃), magnesium silicate (Mg₂SiO₄, MgSiO₃ etc.), magnesiumcalcium silicate (CaMgSiO₄), titanium oxide, titanium dioxide, potassiumtitanate, barium sulfate, zirconium oxide (ZrO₂), zirconium hydroxide[Zr(OH)₂.nH₂O], zirconium carbonate [Zr(CO₃)_(2]), crystallinealuminosilicates, reinforcing grades of zinc oxide (i.e., reinforcingzinc oxide), and combinations thereof.

Silica Coupling Agents

In certain embodiments of the first-third embodiments disclosed herein,the rubber composition includes one or more silica coupling agents.Silica coupling agents are useful in preventing or reducing aggregationof the silica filler in those rubber compositions of the first-thirdembodiments that include a silica filler. Aggregates of the silicafiller particles are believed to increase the viscosity of the rubbercomposition, and, therefore, preventing this aggregation reduces theviscosity and improves the processability and blending of the rubbercomposition.

Generally, any conventional type of silica coupling agent can be used,such as those having a silane and a constituent component or moiety thatcan react with a polymer (rubber), particularly a vulcanizable polymer(rubber). The silica coupling agent acts as a connecting bridge betweensilica and the polymer. Suitable silica coupling agents include thosecontaining groups such as alkyl alkoxy, mercapto, blocked mercapto,sulfide-containing (e.g., monosulfide-based alkoxy-containing,disulfide-based alkoxy-containing, tetrasulfide-basedalkoxy-containing), amino, vinyl, epoxy, and combinations thereof. Incertain embodiments, the silica coupling agent can be added to therubber composition in the form of a pre-treated silica; a pre-treatedsilica has been pre-surface treated with a silane prior to being addedto the rubber composition. The use of a pre-treated silica can allow fortwo ingredients (i.e., silica and a silica coupling agent) to be addedin one ingredient, which generally tends to make rubber compoundingeasier.

Alkyl alkoxysilanes have the general formula R¹ _(p)Si(OR²)_(4-p) whereeach R² is independently a monovalent organic group, and p is an integerfrom 1 to 3, with the proviso that at least one R¹ is an alkyl group.Preferably p is 1. Generally, each R¹ independently comprises C₁ to C₂₀aliphatic, C₅ to C₂₀ cycloaliphatic, or C₆ to C₂₀ aromatic; and each R²independently comprises C₁ to C₆ aliphatic. In certain exemplaryembodiments, each R¹ independently comprises C₆ to C₁₅ aliphatic and inadditional embodiments each R¹ independently comprises C₈ to C₁₄aliphatic. Mercapto silanes have the general formula HS—R³—Si(R⁴)(R⁵)₂where R³ is a divalent organic group, R⁴ is a halogen atom or an alkoxygroup, each R⁵ is independently a halogen, an alkoxy group or amonovalent organic group. The halogen is chlorine, bromine, fluorine, oriodine. The alkoxy group preferably has 1-3 carbon atoms. Blockedmercapto silanes have the general formula B—S—R⁶—Si—X₃ with an availablesilyl group for reaction with silica in a silica-silane reaction and ablocking group B that replaces the mercapto hydrogen atom to block thereaction of the sulfur atom with the polymer. In the foregoing generalformula, B is a block group which can be in the form of an unsaturatedheteroatom or carbon bound directly to sulfur via a single bond; R⁶ isC₁ to C₆ linear or branched alkylidene and each X is independentlyselected from the group consisting of C₁ to C₄ alkyl or C₁ to C₄ alkoxy.

Non-limiting examples of alkyl alkoxysilanes suitable for use in therubber compositions of certain exemplary embodiments according to thefirst-third embodiments disclosed herein include, but are not limitedto, octyltriethoxysilane, octyltrimethoxysilane, trimethylethoxysilane,cyclohexyltriethoxysilane, isobutyltriethoxy-silane,ethyltrimethoxysilane, cyclohexyl-tributoxysilane,dimethyldiethoxysilane, methyltriethoxysilane, propyltriethoxysilane,hexyltriethoxysilane, heptyltriethoxysilane, nonyltriethoxysilane,decyltriethoxysilane, dodecyltriethoxysilane, tetradecyltriethoxysilane,octadecyltriethoxysilane, methyloctyldiethoxysilane,dimethyldimethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane,hexyltrimethoxysilane, heptyltrimethoxysilane, nonyltrimethoxysilane,decyltrimethoxysilane, dodecyltrimethoxysilane,tetradecyltrimethoxysilane, octadecyl-trimethoxysilane, methyloctyldimethoxysilane, and mixtures thereof.

Non-limiting examples of bis(trialkoxysilylorgano)polysulfides suitablefor use in the rubber compositions of certain exemplary embodimentsaccording to the first-third embodiments disclosed herein includebis(trialkoxysilylorgano) disulfides andbis(trialkoxysilylorgano)tetrasulfides. Specific non-limiting examplesof bis(trialkoxysilylorgano)disulfides suitable for use in the rubbercompositions of certain exemplary embodiments according to thefirst-third embodiments disclosed herein include, but are not limitedto, 3,3′-bis(triethoxysilylpropyl) disulfide,3,3′-bis(trimethoxysilylpropyl)disulfide,3,3′-bis(tributoxysilylpropyl)disulfide,3,3′-bis(tri-t-butoxysilylpropyl)disulfide,3,3′-bis(trihexoxysilylpropyl)disulfide,2,2′-bis(dimethylmethoxysilylethyl)disulfide,3,3′-bis(diphenylcyclohexoxysilylpropyl)disulfide,3,3′-bis(ethyl-di-sec-butoxysilylpropyl)disulfide,3,3′-bis(propyldiethoxysilylpropyl)disulfide,12,12′-bis(triisopropoxysilylpropyl)disulfide,3,3′-bis(dimethoxyphenylsilyl-2-methylpropyl)disulfide, and mixturesthereof. Non-limiting examples of bis(trialkoxysilylorgano)tetrasulfidesilica coupling agents suitable for use in the rubber compositions ofcertain exemplary embodiments according to the first-third embodimentsdisclosed herein include, but are not limited to,bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasufide, bis(3-trimethoxysilylpropyl)tetrasulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide,2-triethoxysilyl-N,N-dimethylthiocarbamoyl tetrasulfide,3-trimethoxysilylpropyl-benzothiazole tetrasulfide,3-triethoxysilylpropylbenzothiazole tetrasulfide, and mixtures thereof.Bis(3-triethoxysilylpropyl)tetrasulfide is sold commercially as Si69® byEvonik Degussa Corporation.

Non-limiting examples of mercapto silanes suitable for use in the rubbercompositions of certain exemplary embodiments of the first-thirdembodiments disclosed herein include, but are not limited to,1-mercaptomethyltriethoxysilane, 2- mercaptoethyltriethoxysilane,3-mercaptopropyltriethoxysilane, 3- mercaptopropylmethyldiethoxysilane,2-mercaptoethyltripropoxysilane, 18-mercaptooctadecyldiethoxychlorosilane, and mixtures thereof.

Non-limiting examples of blocked mercapto silanes suitable for use inthe rubber compositions of certain exemplary embodiments according tothe first-third embodiments disclosed herein include, but are notlimited to, those described in U.S. Pat. Nos. 6,127,468; 6,204,339;6,528,673; 6,635,700; 6,649,684; and 6,683,135, the disclosures of whichare hereby incorporated by reference. Representative examples of theblocked mercapto silanes for use herein in certain exemplary embodimentsdisclosed herein include, but are not limited to,2-triethoxysilyl-1-ethylthioacetate;2-trimethoxysilyl-1-ethylthioacetate;2-(methyldimethoxysilyl)-1-ethylthioacetate;3-trimethoxysilyl-1-propylthioacetate; triethoxysilylmethyl-thioacetate;trimethoxysilylmethylthioacetate; triisopropoxysilylmethylthioacetate;methyldiethoxysilylmethylthioacetate;methyldimethoxysilylmethylthioacetate;methyldiisopropoxysilylmethylthioacetate;dimethylethoxysilylmethylthioacetate;dimethylmethoxysilylmethylthioacetate;dimethylisopropoxysilylmethylthioacetate;2-triisopropoxysilyl-1-ethylthioacetate;2-(methyldiethoxysilyl)-1-ethylthioacetate,2-(methyldiisopropoxysilyl)-1- ethylthioacetate;2-(dimethylethoxysilyl-1-ethylthioacetate; 2-(dimethylmethoxysilyl)-1-ethylthioacetate; 2-(dimethylisopropoxysilyl)-1-ethylthioacetate;3-triethoxysilyl-1-propylthioacetate;3-triisopropoxysilyl-1-propylthioacetate;3-methyldiethoxysilyl-1-propyl-thioacetate;3-methyldimethoxysilyl-1-propylthioacetate;3-methyldiisopropoxysilyl-1-propylthioacetate; 1-(2-triethoxysilyl-1-ethyl)-4-thioacetylcyclohexane;1-(2-triethoxysilyl-1-ethyl)-3- thioacetylcyclohexane;2-triethoxysilyl-5-thioacetylnorbornene;2-triethoxysilyl-4-thioacetylnorbornene;2-(2-triethoxysilyl-1-ethyl)-5-thioacetylnorbornene;2-(2-triethoxy-silyl-1- ethyl)-4-thioacetylnorbornene;1-(1-oxo-2-thia-5-triethoxysilylphenyl)benzoic acid; 6-triethoxysilyl-1-hexylthioacetate; 1-triethoxysilyl-5-hexylthioacetate;8-triethoxysilyl-1- octylthioacetate;1-triethoxysilyl-7-octylthioacetate;6-triethoxysilyl-1-hexylthioacetate; 1-triethoxysilyl-5-octylthioacetate; 8-trimethoxysilyl-1-octylthioacetate;1-trimethoxysilyl-7- octylthioacetate;10-triethoxysilyl-1-decylthioacetate;1-triethoxysilyl-9-decylthioacetate; 1-triethoxysilyl-2-butylthioacetate; 1-triethoxysilyl-3-butylthioacetate;1-triethoxysilyl-3-methyl-2- butylthioacetate;1-triethoxysilyl-3-methyl-3-butylthioacetate; 3-trimethoxysilyl-1-propylthiooctanoate; 3-triethoxysilyl-1-propyl-1-propylthiopalmitate;3-triethoxysilyl-1- propylthiooctanoate;3-triethoxysilyl-1-propylthiobenzoate; 3-triethoxysilyl-1-propylthio-2-ethylhexanoate; 3-methyldiacetoxysilyl-1-propylthioacetate;3-triacetoxysilyl-1- propylthioacetate;2-methyldiacetoxysilyl-1-ethylthioacetate; 2-triacetoxysilyl-1-ethylthioacetate; 1-methyldiacetoxysilyl-1-ethylthioacetate;1-triacetoxysilyl-1-ethyl-thioacetate;tris-(3-triethoxysilyl-1-propyl)trithiophosphate;bis-(3-triethoxysilyl-1- propyl)methyldithiophosphonate;bis-(3-triethoxysilyl-1-propyl)ethyldithiophosphonate; 3-triethoxysilyl-1-propyldimethylthiophosphinate;3-triethoxysilyl-1-propyldiethylthiophosphinate;tris-(3-triethoxysilyl-1-propyl)tetrathiophosphate;bis-(3-triethoxysilyl-1 propyl)methyltrithiophosphonate;bis-(3-triethoxysilyl-1-propyl)ethyltrithiophosphonate; 3-triethoxysilyl-1-propyldimethyldithiophosphinate;3-triethoxysilyl-1-propyldiethyldithiophosphinate;tris-(3-methyldimethoxysilyl-1-propyl)trithiophosphate;bis-(3-methyldimethoxysilyl- 1-propyl)methyldithiophosphonate;bis-(3-methyldimethoxysilyl-1-propyl)-ethyldithiophosphonate;3-methyldimethoxysilyl-1-propyldimethylthiophosphinate; 3-methyldimethoxysilyl-1-propyldiethylthiophosphinate;3-triethoxysilyl-1-propylmethylthiosulfate;3-triethoxysilyl-1-propylmethanethiosulfonate;3-triethoxysilyl-1-propylethanethiosulfonate;3-triethoxysilyl-1-propylbenzenethiosulfonate;3-triethoxysilyl-1-propyltoluenethiosulfonate;3-triethoxysilyl-1-propylnaphthalenethiosulfonate;3-triethoxysilyl-1-propylxylenethiosulfonate;triethoxysilylmethylmethylthiosulfate;triethoxysilylmethylmethanethiosulfonate;triethoxysilylmethylethanethiosulfonate;triethoxysilylmethylbenzenethiosulfonate;triethoxysilylmethyltoluenethiosulfonate;triethoxysilylmethylnaphthalenethiosulfonate;triethoxysilylmethylxylenethiosulfonate, and the like. Mixtures ofvarious blocked mercapto silanes can be used. A further example of asuitable blocked mercapto silane for use in certain exemplaryembodiments is NXT™ silane (3-octanoylthio-1-propyltriethoxysilane),commercially available from Momentive Performance Materials Inc. ofAlbany, NY.

Non-limiting examples of pre-treated silicas (i.e., silicas that havebeen pre-surface treated with a silane) suitable for use in the rubbercompositions of certain exemplary embodiments according to thefirst-third embodiments disclosed herein include, but are not limitedto, Ciptane® 255 LD and Ciptane® LP (PPG Industries) silicas that havebeen pre-treated with a mercaptosilane, and Coupsil® 8113 (Degussa) thatis the product of the reaction between organosilaneBis(triethoxysilylpropyl) polysulfide (Si69) and Ultrasil® VN3 silica.Coupsil 6508, Agilon 400 ™ silica from PPG Industries, Agilon 454®silica from PPG Industries, and 458® silica from PPG Industries. Inthose embodiments of the rubber compositions and methods disclosedherein where the silica comprises a pre-treated silica, the pre-treatedsilica is used in an amount as previously disclosed for the reinforcingsilica filler (i.e., about 5 to about 200 phr, including 5 to 200 phr,about 10 to about 200 phr, 10 to 200 phr, about 10 to about 175 phr, 10to 175 phr, about 25 to about 150 phr, 25 to 150 phr, about 35 to about150 phr, 35 to 150 phr, about 25 to about 125 phr, 25 to 125 phr, about25 to about 100 phr, 25 to 100 phr, about 25 to about 80 phr, 25 to 80phr, about 35 to about 125 phr, 35 to 125 phr, about 35 to about 100phr, 35 to 100 phr, about 35 to about 80 phr, and 35 to 80 phr about 5to about 200 phr, including about 25 to about 150 phr, about 35 to about150 phr, about 25 to about 125 phr, about 25 to about 100 phr, about 25to about 80 phr, about 35 to about 125 phr, about 35 to about 100 phr,and about 35 to about 80 phr).

When a silica coupling agent is utilized, the amount of silica couplingagent used in the rubber compositions according to the first-thirdembodiments disclosed herein may vary. In certain embodiments of thefirst-third embodiments disclosed herein, the rubber compositions do notcontain any silica coupling agent. In other embodiments of thefirst-third embodiments disclosed herein, the silica coupling agent ispresent in an amount sufficient to provide a ratio of the total amountof silica coupling agent to reinforcing silica filler of about 1:100 toabout 1:5 (i.e., about 0.01 to about 20 parts by weight per 100 parts ofsilica), including 1:100 to 1:5, about 1:100 to about 1:10, 1:100 to1:10, about 1:100 to about 1:20, 1:100 to 1:20, about 1:100 to about1:25, and 1:100 to 1:25 as well as about 1:100 to about 0:100 and 1:100to 0:100. In certain embodiments according to the first-thirdembodiments disclosed herein, the rubber composition comprises about0.01 to about 10 phr silica coupling agent, including 0.01 to 10 phr,about 0.01 to about 5 phr, 0.01 to 5 phr, about 0.01 to about 3 phr, and0.01 to 3 phr.

Other Components of the Rubber Composition

In certain embodiments of the first-third embodiments, the rubbercomposition includes (i.e., further comprises) a cure package.Generally, the cure package includes at least one of: a vulcanizingagent; a vulcanizing accelerator; a vulcanizing activator (e.g., zincoxide, stearic acid, and the like); a vulcanizing inhibitor, and ananti-scorching agent. In certain embodiments, the cure package includesat least one vulcanizing agent, at least one vulcanizing accelerator, atleast one vulcanizing activator and optionally a vulcanizing inhibitorand/or an anti-scorching agent. Vulcanizing accelerators and vulcanizingactivators act as catalysts for the vulcanization agent. Vulcanizinginhibitors and anti-scorching agents are known in the art and can beselected by one skilled in the art based on the vulcanizate propertiesdesired.

Examples of suitable types of vulcanizing agents for use in the rubbercompositions according to certain embodiments of the first-thirdembodiments, include but are not limited to, sulfur or peroxide-basedcuring components. Thus, in certain such embodiments, the curativecomponent includes a sulfur-based curative or a peroxide-based curative.Examples of specific suitable sulfur vulcanizing agents include“rubbermaker’s” soluble sulfur; sulfur donating curing agents, such asan amine disulfide, polymeric polysulfide, or sulfur olefin adducts; andinsoluble polymeric sulfur. Preferably, the sulfur vulcanizing agent issoluble sulfur or a mixture of soluble and insoluble polymeric sulfur.For a general disclosure of suitable vulcanizing agents and othercomponents used in curing, e.g., vulcanizing inhibitor andanti-scorching agents, one can refer to Kirk-Othmer, Encyclopedia ofChemical Technology, 3rd ed., Wiley Interscience, N.Y. 1982, Vol. 20,pp. 365 to 468, particularly Vulcanization Agents and AuxiliaryMaterials, pp. 390 to 402, or Vulcanization by A. Y. Coran, Encyclopediaof Polymer Science and Engineering, Second Edition (1989 John Wiley &Sons, Inc.), both of which are incorporated herein by reference.Vulcanizing agents can be used alone or in combination. Generally, thevulcanizing agents are used in an amount ranging from 0.1 to 10 phr,including from 1 to 7.5 phr, including from 1 to 5 phr, and preferablyfrom 1 to 3.5 phr.

Vulcanizing accelerators are used to control the time and/or temperaturerequired for vulcanization and to improve properties of the vulcanizate.Examples of suitable vulcanizing accelerators for use in the rubbercompositions according to certain embodiments of the first-thirdembodiments disclosed herein include, but are not limited to, thiazolevulcanization accelerators, such as 2-mercaptobenzothiazole,2,2′-dithiobis(benzothiazole) (MBTS),N-cyclohexyl-2-benzothiazole-sulfenamide (CBS),N-tert-butyl-2-benzothiazole-sulfenamide (TBBS), and the like; guanidinevulcanization accelerators, such as diphenyl guanidine (DPG) and thelike; thiuram vulcanizing accelerators; carbamate vulcanizingaccelerators; and the like. Generally, the amount of the vulcanizationaccelerator used ranges from 0.1 to 10 phr, preferably 0.5 to 5 phr.

Vulcanizing activators are additives used to support vulcanization.Generally vulcanizing activators include both an inorganic and organiccomponent. Zinc oxide is the most widely used inorganic vulcanizationactivator. Various organic vulcanization activators are commonly usedincluding stearic acid, palmitic acid, lauric acid, and zinc salts ofeach of the foregoing. Generally, the amount of vulcanization activatorused ranges from 0.1 to 6 phr, preferably 0.5 to 4 phr.

Vulcanization inhibitors are used to control the vulcanization processand generally retard or inhibit vulcanization until the desired timeand/or temperature is reached. Common vulcanization inhibitors include,but are not limited to, PVI (cyclohexylthiophthalmide) from Santogard.Generally, the amount of vulcanization inhibitor is 0.1 to 3 phr,preferably 0.5 to 2 phr.

Other ingredients that may be employed in the rubber compositions ofcertain embodiments of the first-third embodiments disclosed herein arewell known to those of skill in the art and include oils (processing andextender), waxes, processing aids, anti-degradants such as antioxidantsand anti-ozonants, tackifying resins, reinforcing resins, fatty acids,peptizers, zinc oxide, and the like. In certain embodiments of thefirst-third embodiments disclosed herein, the rubber compositioncomprises at least one of the following: a processing oil; an extenderoil; a wax; a processing aid; an anti-degradant such as an antioxidant,an anti-ozonant, or both; a tackifying resin; a reinforcing resin; afatty acid or a salt thereof; a peptizer, and zinc oxide; in certainsuch embodiments more than one of each type of ingredient may beutilized (e.g., more than one antioxidant, more than one processing aid,etc.).

Anti-degradants are ingredients added to protect the rubber fromoxidative attack. ASTM D-4676 classifies rubber anti-degradants into sixclasses: p-phenylenediamines (PPDs), trimethyl-dihydroquinolines (TMQs),phenolics, alkylated diphenylamines (DPAs), aromatic phosphites, anddiphenylamine-ketone condensates. In certain embodiments of thefirst-third embodiments disclosed herein, the rubber compositioncomprises at least one of the foregoing anti-degradants.

As discussed above, in certain embodiments of the first-thirdembodiments disclosed herein, the bio-oil from a recombinant cell may beutilized in combination with at least one additional oil (processing,extender or both). When at least one additional oil is utilized (i.e.,in addition to the bio-oil from a recombinant cell) it may be apetroleum oil or a plant-sourced oil. In certain embodiments of thefirst-third embodiments disclosed herein, the rubber composition furthercomprises at least one petroleum oil, at least one plant-sourced oil (inaddition to the bio-oil from a recombinant cell), or both. In certainembodiments of the first-third embodiments disclosed herein, the rubbercomposition is essentially free of any plant oil other than the bio-oilfrom a recombinant cell. In certain embodiments of the first-thirdembodiments disclosed herein, the rubber composition is essentially freeof any petroleum oil. Essentially free of can be understood as a rubbercomposition containing no more than 5 phr, including no more than 1 phr,and 0 phr. Various types of petroleum oils are well known and may besuitable for use as an additional oil (processing, extender, or both) inthe rubber compositions of certain embodiments of the first-thirdembodiment disclosed herein, including, but not limited to aromatic,naphthenic, and low PCA oils. Suitable low PCA oils include those havinga polycyclic aromatic content of less than 3 percent by weight asdetermined by the IP346 method. Procedures for the IP346 method may befound in Standard Methods for Analysis & Testing of Petroleum andRelated Products and British Standard 2000 Parts, 2003, 62nd edition,published by the Institute of Petroleum, United Kingdom. Suitable lowPCA oils include mild extraction solvates (MES), treated distillatearomatic extracts (TDAE), TRAE, and heavy naphthenics. Suitable MES oilsare available commercially as CATENEX SNR from SHELL, PROREX 15, andFLEXON 683 from EXXONMOBIL, VIVATEC 200 from BP, PLAXOLENE MS from TOTALFINA ELF, TUDALEN 4160/4225 from DAHLEKE, MES-H from REPSOL, MES fromZ8, and OLIO MES S201 from AGIP. Suitable TDAE oils are available asTYREX 20 from EXXONMOBIL, VIVATEC 500, VIVATEC 180, and ENERTHENE 1849from BP, and EXTENSOIL 1996 from REPSOL. Suitable heavy naphthenic oilsare available as SHELLFLEX 794, ERGON BLACK OIL, ERGON H2000, CROSSC2000, CROSS C2400, and SAN JOAQUIN 2000L. Preferably, the rubbercomposition of the first-third embodiments is essentially free anypetroleum oil. Suitable low PCA oils also include various plant-sourcedoils such as can be harvested from vegetables, nuts, and seeds.Non-limiting examples include, but are not limited to, soy or soybeanoil, sunflower oil, safflower oil, corn oil, linseed oil, cotton seedoil, rapeseed oil, cashew oil, sesame oil, camellia oil, jojoba oil,macadamia nut oil, coconut oil, and palm oil. The foregoing processingoils can also be used as an extender oil, i.e., to prepare anoil-extended polymer or copolymer. Generally, for most tire and tirecomponent applications the total amount of oil used (processing oil andextender oil) in the rubber compositions and methods disclosed hereinranges from about 5 to about 70 phr, including 5 to 70 phr, about 5 toabout 60 phr, about 5 to about 60 phr, about 5 to about 50 phr, and 5 to50 phr; the total amount of oil should be understood to include both thebio-oil from a recombinant cell and any additional oil. However, incertain tire and tire component applications, the total amount of oilused (processing oil and extender oil) in the rubber compositions andmethods disclosed herein is much higher and ranges up to about 175 phr,including up to 175 phr, up to about 150 phr, up to 150 phr, up to about100 phr, and up to 100 phr.

Methods For Preparing Rubber Compositions

The rubber compositions according to the first-third embodimentsdisclosed herein may generally be formed by mixing together theingredients for the rubber composition (as disclosed above) by methodsknown in the art, such as, for example, by kneading the ingredientstogether in a Banbury mixer or on a milled roll. The methods generallyinclude at least one non-productive master-batch mixing stage and afinal productive mixing stage. The term non-productive master-batchstage is known to those of skill in the art and generally understood tobe a mixing stage where no vulcanizing agents or vulcanizationaccelerators are added. The term final productive mixing stage is alsoknown to those of skill in the art and generally understood to be themixing stage where the vulcanizing agents and vulcanization acceleratorsare added into the rubber composition. In certain embodiments of thecompositions and methods disclosed herein, more than one non-productivemaster-batch mixing stage may be used. In certain embodiments of thecompositions and methods disclosed herein, more than one non-productivemaster-batch mixing stage is used and the bio-oil from a recombinantcell is added in the first (initial) master-batch stage. In otherembodiments of the compositions and methods disclosed herein, at leasttwo non-productive master-batch mixing stages are used and the bio-oilfrom a recombinant cell is added in the second master-batch stage. Inother embodiments of the compositions and methods disclosed herein, atleast two non-productive master-batch mixing stages are used and thebio-oil from a recombinant cell is added in more than one master-batchstage. In yet other embodiments of the compositions and methodsdisclosed herein, more than one non-productive master-batch mixing stageis used and the bio-oil from a recombinant cell is added in the lastnon-productive master-batch mixing stage.

In certain embodiments of the methods for preparing rubber compositionsaccording to the first-third embodiments disclosed herein, thenon-productive master batch mixing stage(s) may be conducted at atemperature of about 130° C. to about 200° C. In certain embodiments,the final productive mixing stage may be conducted at a temperaturebelow the vulcanization temperature in order to avoid unwanted pre-cureof the rubber composition. Therefore, the temperature of the productivemixing stage should not exceed about 120° C. and is typically about 40°C. to about 120° C., or about 60° C. to about 110° C. and, especially,about 75° C. to about 100° C.

In certain embodiments of the first-third embodiments disclosed herein,a rubber composition is prepared according to a method that includes atleast one non-productive mixing stage and at least one productivemixture stage. In certain embodiments, the method for preparing therubber compositions of the present disclosure includes: (1) mixing, inat least one non-productive master-batch stage, a rubber compositioncomprising: 100 phr of at least one rubber; from about 5 to about 200phr (including 5 to 200 phr) of at least one reinforcing filler; andabout 5 to about 50 phr of bio-oil from a recombinant cell; and (2)mixing the resulting product of the non-productive master batch in afinal productive stage along with at least one curative, such as acurative package, as discussed above. With respect to certainembodiments of the first embodiment disclosed herein, the list ofingredients should be understood as including ingredients to be mixed toform the rubber composition. With respect to the certain embodiments ofthe second embodiment disclosed herein (i.e., a rubber composition thathas been subjected to curing), the list of ingredients should beunderstood to comprise the ingredients present in the cured rubbercomposition.

Tires and Tire Components

As previously discussed, certain embodiments disclosed herein includetires, tire treads, and tire sidewalls comprising a rubber compositionof the second embodiments as otherwise disclosed herein, i.e.,comprising at least one rubber and about 5 to about 50 phr of bio-oilfrom a recombinant cell. More specifically, the present disclosureincludes a tire comprising a rubber composition of the first-thirdembodiments as otherwise disclosed herein, a tire comprising a tiretread comprising a rubber composition of the first-third embodiments asotherwise disclosed herein, a tire tread comprising a rubber compositionof the first-third embodiments as otherwise disclosed herein, a tirecomprising a tire sidewall comprising a rubber composition of thefirst-third embodiments as otherwise disclosed herein, and a tiresidewall comprising a rubber composition of the first-third embodimentsas otherwise disclosed herein. Generally, when the rubber compositionsof the first-third embodiments disclosed herein are utilized in tires,tire treads, or tire sidewalls, these compositions are processed intotire components according to ordinary tire manufacturing techniquesincluding standard rubber shaping, molding, and curing techniques. Anyof the various rubber tire components can be fabricated including, butnot limited to, treads, sidewalls, belt skims, and carcass. Typically,vulcanization of a tire component is effected by heating thevulcanizable composition in a mold; e.g., it may be heated to about 140°C. to about 180° C. Cured or crosslinked rubber compositions may bereferred to as vulcanizates, which generally contain three-dimensionalpolymeric networks that are thermoset. The other ingredients, such asprocessing aides and fillers, may be evenly dispersed throughout thevulcanized network. In certain embodiments, pneumatic tires containingthe rubber compositions as disclosed herein can be produced as discussedin U.S. Pat. Nos. 5,866,171, 5,876,527, 5,931,211, and 5,971,046, whichare incorporated herein by reference.

Methods of Controlling the Variability of Fatty Acid Content

As discussed above, in a first embodiment, a method is disclosed forcontrolling the variability of fatty acid content in abio-oil-containing rubber composition. The method comprisesincorporating about 5 to about 100 phr of bio-oil produced by arecombinant cell with at least one rubber, at least one reinforcingfiller, and a cure package, thereby forming a bio-oil-containing rubbercomposition. By the method of the first embodiment, a bio-oil producedby a recombinant cell is used in a rubber composition instead of (or incertain embodiments in addition to) a bio-oil obtained from a plant. Theuse of bio-oil produced by a recombinant cell such as an algal cellcontrols (or reduces) the variability in fatty acid content that wouldotherwise occur when a plant-sourced bio-oil is utilized. Plant-sourcedbio-oils can vary widely in fatty acid content depending upon variousconditions such as time of planting, weather conditions, and location ofthe crop. For example, according to Robertson, et al., “Effect ofPlanting Date on Sunflower Seed Content, Fatty Acid Composition andYield in Florida,” Journal of the American Oil Chemists’ Society, June1981, Volume 58, Issue 6, pp 698-701, time of planting at the samelocation caused the mean oleic acid content in sunflower seeds to varyfrom 54.6% (April 2 planting) to 19.4% (August 14 planting) and thelinoleic acid content to vary from 36.3% (April 2 planting) to 68.4%(August 14 planting). Similarly, Unger reported on the variation inoleic acid and linoleic acid content in sunflowers grown in northernTexas, finding a variation in oleic acid content of from 16.3% (July28-August 1 planting) to 44.8% (April 17-26 planting) and a variation inlinoleic acid content of from 71.6% (July 15-19 planting) to 43.3%(April 17-26 planting). “Planting Date Effects On Growth, Yield, And Oilof Irrigated Sunflower,” Agronomy Journal, vol. 72, Nov.-December 1980,pp. 914-16. Thus, plant-sourced bio-oils can vary in fatty acid contentby more than 100%, sometimes more than 200%, and in certain instances asmuch as almost 300%. Such variations can make quality control or meetingan internal specification for a plant-sourced bio-oil difficult tomaintain within acceptable limits. The use of a bio-oil produced by arecombinant cell such as an algal cell can alleviate this difficulty byproviding a bio-oil with little, if any, variation in fatty acidcontent. In certain embodiments, the bio-oil produced by a recombinantcell has a variation in the content of a particular fatty acid of lessthan +/- 5%, preferably less than +/- 3%, and more preferably less than+/- 1% (the percentages being determined based upon the particularamount of fatty acid so that a content that averages 20% oleic acid butranges from 16% to 24% would be considered to have a variation of +/-20%).

Methods of Providing a Bio-Oil Containing Tire With A Reduced CarbonFootprint

In a second embodiment, a method is disclosed for providing abio-oil-containing tire with a reduced carbon footprint. The methodcomprises incorporating about 5 to about 100 phr of bio-oil produced bya recombinant cell into at least one rubber, at least one reinforcingfiller, and a cure package, thereby forming an oil-containing rubbercomposition, and incorporating the oil-containing rubber compositioninto at least one component of a tire, thereby producing a reducedcarbon footprint oil containing tire. By the method of the secondembodiment, a bio-oil produced by a recombinant cell is used in a rubbercomposition instead of a bio-oil obtained from a plant. A significantamount of fossil fuel products (e.g., gasoline, oil, and products suchas fertilizers made therefrom) are expended growing and harvest plantsto produce bio-oils. The use of bio-oils produced by recombinant cellssuch as algal cells offers a source of bio-oil that is produced using alesser amount of fossil fuel products. Accordingly, the incorporation ofbio-oil produced by a recombinant cell into a rubber composition and theincorporating of the oil-containing rubber composition into at least onecomponent of a tire, will result in a tire having a reduced carbonfootprint. The phrase reduced carbon footprint should be understood toinclude not only the amount of petroleum-based products used in thetire, but also the amount of fossil fuel products used to produce thebio-oil(s) contained within the tire.

EXAMPLES

The following examples illustrate specific and exemplary embodimentsand/or features of the embodiments of the present disclosure. Theexamples are provided solely for the purposes of illustration and shouldnot be construed as limitations of the present disclosure. Numerousvariations over these specific examples are possible without departingfrom the spirit and scope of the presently disclosed embodiments. Morespecifically, the particular rubbers, fillers, and other ingredients(e.g., antioxidant, and curative package ingredients) utilized in thefollowing examples should not be interpreted as limiting since othersuch ingredients consistent with the disclosure in the DetailedDescription can be utilized in substitution. In other words, theparticular rubbers, fillers, and other ingredients as well as theiramounts and their relative amounts in the following examples should beunderstood to apply to the more general content of the DetailedDescription.

Examples 1 to 8

In Examples 1 to 8, rubber compositions were prepared comprising rubber(natural rubber in combination with one of: solution SBR, high-cispolybutadiene, low-cis polybutadiene, or functionalized SBR), carbonblack filler, and either a petroleum oil or a bio-oil produced by arecombinant (algal) cell. The functionalized SBR was functionalized withtin, producing a carbon-black reactive polymer. The bio-oil produced bya recombinant (algal) cell was obtained from Solazyme, Inc. (SanFrancisco, California), under their designation S3168; the oil isreferred to within the Tables as “Algal oil.” The rubber compositions ofExamples 1 to 8 were prepared in a four stage mixing process (i.e., onemaster-batch stage, and a final batch stage) according to theformulations shown in Table 1A. The amount of each ingredient used isreported as parts per hundred rubber (phr). The mixing processes usedfor these formulations are outlined in Table 1B. The indexed datareported in Table 1C has been prepared relative to the data for therespective control composition (e.g., Example 1 is the control forExample 2, Example 3 is the control for Example 4, Example 5 is thecontrol for Example 6, and Example 7 is the control for Example 8), andcalculated so that an improvement (i.e., a movement in a propertytowards a more desirable measurement) appears as a number greater than 1and a property that moves towards a less desirable measurement appearsas a number less than 1. Such an indexing system was used to account forthe fact that for some properties an increase in the measured value isdesirable whereas for other properties a decrease in the measured valueis desirable. Properties deemed to show an improvement when the valueincreased are indicated using the symbol ^ in Table 1C.

TABLE 1A Formulation matrix for algal oil with four polymeric systemswith carbon black Stocks# 1 sSBR w/proc. oil 2 sSBR w/algal oil 3high-cis BR w/proc. oil 4 high-cis BR w/algal oil 5 low-cis BR w/proc.oil 6 low-cis BR w/algal oil 7 CB-func. Poly. w/proc. oil 8 CB-func.Poly. w/algal oil Master-Batch #1 s-SBR¹ 80 80 0 0 0 0 0 0 High-cisPolybutadiene² 0 0 80 80 0 0 0 0 Low-cis Polybutadiene³ 0 0 0 0 80 80 00 Functionalized Polymer⁴ 0 0 0 0 0 0 80 80 Natural Rubber 20 20 20 2020 20 20 20 Carbon black 50 50 50 50 50 50 50 50 Processing oil⁵ 10 1010 10 Bio-oil from Recombinant cell⁶ 0 10 0 10 0 10 0 10 Curative #1 2 22 2 2 2 2 2 Antioxidant/ Anti degradant 2.95 2.95 2.95 2.95 2.95 2.952.95 2.95 Final Batch Curative #2 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5Vulcanizing agent 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Vulcanizationaccelerators 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 ¹ Styrene-butadienecopolymer prepared by solution polymerization and containing 23.5%styrene. ² High-cis polybutadiene (96% cis)′ ³ Low-cis polybutadiene(33% cis). ⁴ Styrene butadiene copolymer or polybutadiene, tinfunctionalized. ⁵ Low PCA oil, Black Oil from Ergon Manufacturing. ⁶This oil contained 80% oleic acid, 8% linoleic acid, 0.3%alpha-linolenic, with 9% saturated fatty acids having C10-C24 and lessthan 0.1% free fatty acids.

TABLE 1B Mixing Parameters for carbon black-containing compositionsStage Time Condition Master-Batch Stage 1 (initial temp: 160° C., rotorrpm started at 115) 0 seconds Charge polymers 15 seconds Charge any oil,filler (e.g., any carbon black) and other master-batch ingredients Dropram after 120 seconds Final Batch Stage (initial temp: 98° C., rotor rpmat 40) 0 seconds 0 seconds Charge curatives, AO, accelerators Drop basedon max temperature of 210° F. (99° C.)

Each of the rubber compositions was subjected to testing to measurevarious properties. Results are reported below in Table 1C. Samples weretested by tensile testing to measure the elastic properties of thecomposition. The abbreviation E_(b) is used for elongation at break andT_(b) for stress at break, which measurements provides an indication ofa rubber component’s tear resistance, which is particularly relevantwhen it is incorporated into a tire tread. The abbreviation M300 is usedfor the tensile stress measured at 300% elongation.

Tensile mechanical properties of the samples were determined followingthe guidelines, but not restricted to, the standard procedure describedin ASTM D-412, using dumbbell-shaped samples with a cross-sectiondimension of 4 mm in width and 1.9 mm in thickness at the center.Specimens were strained at a constant rate and the resulting force wasrecorded as a function of extension (strain). The specimens were testedat 23° C. The elongation at break was measured after 40 minutes andafter sweeping the temperature from either 25° C. or 100° C. to 150° C.Samples were cured for 40 minutes at 150° C., and then tensileproperties were analyzed at 25° C. and at 100° C.

Tan δ values were measured using a dynamic compression test done with aDynastat™ mechanical spectrometer (Dynastatics Instruments Corp.;Albany, New York) using a cylindrical button geometry test specimen (7.8mm diameter x 6 mm height). The temperature was held constant at thedesired temperature: 0° C., 30° C., or 60° C. The sample was compressedunder a static load of 2 kg before testing. After it reached anequilibrium state, the test started with a dynamic compression load of1.25 kg at a frequency of 15 Hz. The sample was then dynamicallycompressed and then extended and the resultant hysteresis (tan δ) wasthen recorded. A rubber composition’s tan δ at 0° C. is indicative ofits wet traction when incorporated into a tire tread, its tan δ at 30°C. is indicative of its dry traction when incorporated into a tire treadand its tan δ at 60° C. is indicative of its rolling resistance whenincorporated into a tire tread.

The viscosities disclosed herein are real dynamic viscosities determinedusing an Alpha Technologies RPA (Rubber Process Analyzer) instrumentwhich is rotorless. Measurements were made following the guidance of,but not strictly according to ASTM D 6204. In accordance with ASTM D6204, a three point frequency sweep was conducted. The rubbercompositions were pre-heated for 1 minute at 130° C. . In accordancewith the ASTM procedure, strain sweep was conducted at 130 C,, strain at100 percent, and 1 Hz were conducted. The viscosity data reported isfrom a run conducted at 266° F., G′ at 2 minutes.

TABLE 1C Property 1 sSBR w/proc. oil 2 sSBR w/algal oil 3 high cis BR w/proc. oil 4 high cis BR w/ algal oil 5 low cis BR w/ proc. oil 6 low cisBR w/ algal oil 7 funct. Poly w/ proc. oil 8 funct. Poly w/ algal oilIndexed M300^ 1.00 0.95 1.00 0.89 1.00 0.91 1.00 0.90 Indexed Tb^ 1.000.88 1.00 0.91 1.00 0.86 1.00 0.70 Indexed Eb^ 1.00 1.01 1.00 1.02 1.000.95 1.00 0.85 Indexed tan δ 0° C.^ 1.00 0.95 1.00 0.97 1.00 0.97 1.000.96 Indexed tan δ 30° C.^ 1.00 0.97 1.00 0.96 1.00 0.98 1.00 0.99Indexed E′^ 1.00 0.89 1.00 0.80 1.00 0.875 1.00 0.95 Indexed tan δ 60°C. 1.00 1.02 1.00 1.04 1.00 1.02 1.00 0.99 Indexed viscosity 1.00 1.031.00 1.02 1.00 0.99 1.00 0.99 Indexed wear 1.00 1.11 100 1.27 1.00 1.111.00 1.16

As can be seen from the data in Table 1C, the addition of bio-oilproduced by a recombinant (algal) cell to any of the four rubbercompositions results in an improvement in the wear rate (i.e., reducedwear) for all four rubber types; an improvement to comparable Tb in thecomposition containing high-cis BR; an improvement to comparable Eb inthe compositions comprising SBR, high-cis BR, or low-cis BR; animprovement to comparable tan δ at 0° C. for all four rubber types; animprovement to comparable tan δ at 30° C. for all four rubber types; animprovement to comparable E′ for the composition comprisingfunctionalized polymer; an improvement to comparable tan δ at 60° C. forall four rubber types; and an improvement to comparable effect onviscosity for all four rubber types. (Comparable being used as includingan index value of no less than 0.9.)

Examples 9 to 16

In Examples 9 to 16, rubber compositions were prepared comprising rubber(natural rubber in combination with one of: solution SBR (s-SBR),high-cis polybutadiene, low-cis polybutadiene, or functionalized SBR),silica filler, and either a petroleum-based processing oil or a bio-oilproduced by a recombinant (algal) cell. The functionalized SBR containedsilica-reactive functionality, producing a silica-reactive polymer. Thebio-oil produced by a recombinant (algal) cell was obtained fromSolazyme, Inc. (San Francisco, California), under their designationS3168; the oil is referred to within the Tables as “Algal oil.” Therubber compositions of Examples 9 to 16 were prepared in a four stagemixing process (i.e., two master-batch stages, a remill, and a finalbatch stage) according to the formulations shown in Table 2A. The amountof each ingredient used is reported as parts per hundred rubber (phr).The mixing processes used for these formulations are outlined in Table2B. The indexed data reported in Table 2C was prepared in the samemanner described above for Example 1 to 8.

TABLE 2 A - Formulation matrix for algal oil with four polymeric systemswith silica Stocks# 1 sSBR w/proc. oil 2 sSBR w/algal oil 3 high-cis BRw/proc. oil 4 high-cis BR w/algal oil 5 low-cis BR w/proc. oil 6 low-cisBR w/algal oil 7 silica-func. Poly. w/proc. oil 8 silica func. Poly.w/algal oil Master-Batch #1 s-SBR¹ 80 80 0 0 0 0 0 0 High-cisPolybutadiene² 0 0 80 80 0 0 00 Low-cis Polybutadiene³ 0 0 0 0 80 80 0 0Functionalized Polymer⁴ 0 0 0 0 0 0 80 80 Natural rubber 20 20 20 20 2020 20 20 Silica filler 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5Processing oil⁵ 10 0 10 0 10 0 10 0 Algal oil⁶ 0 10 0 10 0 10 0 10Curative #1 0 0.6 1.2 0 0.6 1.2 0.6 1.2 Antioxidant/ Antidegradant 4 4 44 4 4 4 4 Master-Batch #2 Silica 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Silicacoupling agent (silane) 5 5 5 5 5 5 5 5 Final Batch Curative #2 2.5 2.52.5 2.5 2.5 2.5 2.5 2.5 Vulcanizing agent 1.5 1.5 1.5 1.5 1.5 1.5 1.51.5 Vulcanization accelerators 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 ¹Styrene-butadiene copolymer prepared by solution polymerization andcontaining 23.5% styrene. ² High-cis polybutadiene (96% cis)′ ³ Low-cispolybutadiene (33% cis). ⁴ Styrene-butadiene copolymer with silicareactive functionality. ⁵ Low PCA oil, Black Oil from ErgonManufacturing. ⁶ This oil contained 80% oleic acid, 8% linoleic acid,0.3% alpha-linolenic, with 9% saturated fatty acids having C10-C24 andless than 0.1 % free fatty acids.

TABLE 2B Mixing Parameters for silica-containing compositions Stage TimeCondition Master-Batch Stage 1 (initial temp: 105° C., rotor rpm startedat 60) 0 seconds Charge polymers 30 seconds Charge any oil, filler(e.g., any carbon black and/or silica) and other master-batchingredients, increase rotor to 75 rpm Drop based on max temperature of310° F. (154° C.) Master-Batch Stage 2 (initial temp: 105° C., rotor rpmstarted at 60) 0 seconds Charge additional ingredients listed underMaster-Batch #2 Drop based on max temperature of 300° F. (149° C.)Remill Stage (initial temp: 105° C., rotor rpm at 60 ) 0 seconds ChargeMaster Batch from #2 Drop based on max temperature of 300° F. (149° C.)Final Batch Stage (initial temp: 80° C., rotor rpm at 40 ) 0 secondsCharge Remill 0 seconds Charge curatives Drop based on max temperatureof 210° F. (99° C.)

TABLE 2C Property 1 sSBR w/proc. oil 2 sSBR w/algal oil 3 high cis BR w/proc. oil 4 high cis BR w/ algal oil 5 low cis BR w/ proc. oil 6 low cisBR w/ algal oil 7 funct. Poly w/ proc. oil 8 funct. Poly w/ algal oilIndexed M300^ 1.00 0.92 1.00 0.92 1.00 1.02 1.00 0.85 Indexed Tb^ 1.000.96 1.00 1.00 1.00 0.82 1.00 1.09 Indexed Eb^ 1.00 1.02 1.00 1.10 1.000.73 1.00 1.21 Indexed tan δ 0° C.^ 1.00 0.91 1.00 0.79 1.00 1.05 1.000.84 Indexed tan δ 30° C.^ 1.00 1.00 1.00 0.99 1.00 1.02 1.00 0.92Indexed E′^ 1.00 0.95 1.00 0.99 1.00 1.19 1.00 1.11 Indexed tan δ 60° C.1.00 0.99 1.00 1.02 1.00 1.04 1.00 0.97 Indexed viscosity 1.00 1.01 1.001.06 1.00 1.05 1.00 1.02 Indexed wear 1.00 1.08 1.00 1.52 1.00 1.20 1.001.20

As can be seen from the data in Table 2C, the addition of bio-oilproduced by a recombinant (algal) cell to any of the four rubbercompositions results in an improvement in the wear rate (i.e., reducedwear) for all four rubber types, an improvement to comparable Tb in thecompositions containing SBR, high-cis BR or functionalized polymer; animprovement to comparable Eb in the compositions comprising SBR,high-cis BR, or functionalized polymer; an improvement to comparable tanδ at 0° C. in the compositions comprising SBR or low-cis BR; animprovement to comparable tan δ at 30° C. for all four rubber types; animprovement to comparable E′ for all four rubber types; an improvementto comparable tan δ at 60° C. for all four rubber types; and animprovement in viscosity for all four rubber types. (Comparable beingused as including an index value of no less than 0.9.)

This application discloses several numerical range limitations thatsupport any range within the disclosed numerical ranges, even though aprecise range limitation is not stated verbatim in the specification,because the embodiments of the compositions and methods disclosed hereincould be practiced throughout the disclosed numerical ranges. Withrespect to the use of substantially any plural or singular terms herein,those having skill in the art can translate from the plural to thesingular or from the singular to the plural as is appropriate to thecontext or application. The various singular or plural permutations maybe expressly set forth herein for sake of clarity.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims are generallyintended as “open” terms. For example, the term “including” should beinterpreted as “including but not limited to,” the term “having” shouldbe interpreted as “having at least,” the term “includes” should beinterpreted as “includes but is not limited to.” It will be furtherunderstood by those within the art that if a specific number of anintroduced claim recitation is intended, such an intent will beexplicitly recited in the claim, and in the absence of such recitationno such intent is present. For example, as an aid to understanding, thefollowing appended claims may contain usage of the introductory phrases“at least one” and “one or more” to introduce claim recitations.However, the use of such phrases should not be construed to imply thatthe introduction of a claim recitation by the indefinite articles “a” or“an” limits any particular claim containing such introduced claimrecitation to inventions containing only one such recitation, even whenthe same claim includes the introductory phrases “one or more” or “atleast one” and indefinite articles such as “a” or “an” (e.g., “a” or“an” should typically be interpreted to mean “at least one” or “one ormore”); the same holds true for the use of definite articles used tointroduce claim recitations. In addition, even if a specific number ofan introduced claim recitation is explicitly recited, those skilled inthe art will recognize that such recitation should typically beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, typicallymeans at least two recitations, or two or more recitations).Furthermore, in those instances where a convention analogous to “atleast one of A, B, and C, etc.” is used, in general such a constructionis intended in the sense one having skill in the art would understandthe convention (e.g., “a system having at least one of A, B, and C”would include but not be limited to systems that have A alone, B alone,C alone, A and B together, A and C together, B and C together, and/or A,B, and C together, etc.). It will be further understood by those withinthe art that virtually any disjunctive word or phrase presenting two ormore alternative terms, whether in the description, claims, or drawings,should be understood to contemplate the possibilities of including oneof the terms, either of the terms, or both terms. For example, thephrase “A or B” will be understood to include the possibilities of “A”or “B” or “A and B.”

All references, including but not limited to patents, patentapplications, and non-patent literature are hereby incorporated byreference herein in their entirety.

While various aspects and embodiments of the compositions and methodshave been disclosed herein, other aspects and embodiments will beapparent to those skilled in the art. The various aspects andembodiments disclosed herein are for purposes of illustration and arenot intended to be limiting, with the true scope and spirit beingindicated by the claims.

What is claimed is:
 1. A bio-oil-containing rubber composition,comprising 1 to 200 phr of bio-oil produced by a recombinant cell, atleast one rubber including at least one diene monomer-containing polymeror copolymer, 5 to 200 phr of at least one reinforcing filler, and acure package, wherein the at least one reinforcing filler comprises atleast one of carbon black and silica and the amount of carbon black isno more than 30% by weight of the total amount of reinforcing filler. 2.The rubber composition of claim 1, wherein the recombinant cellcomprises an algal cell.
 3. The rubber composition of claim 1, whereinthe bio-oil is present in an amount of 5 to 100 phr.
 4. The rubbercomposition of claim 1, wherein the bio-oil is present in an amount of 1to 50 phr.
 5. The rubber composition of claim 1, wherein the at leastone rubber comprises a majority by weight of at least one ofpolybutadiene, styrene-butadiene copolymer, natural rubber, andpolyisoprene.
 6. The rubber composition of claim 1, wherein the oilproduced by a recombinant cell comprises at least 90% by weight of oneor more fatty acids.
 7. The rubber composition of claim 1, wherein theoil produced by a recombinant cell has either: at least 50% of itscarbon content as naphthenic carbons, or at least 50% of its carboncontent as paraffinic carbons.
 8. A tire component comprising the rubbercomposition of claim
 5. 9. A tire tread comprising the rubbercomposition of claim
 5. 10. A method for improving at least one of thewear rate or E′ of a rubber composition, the method comprisingincorporating about 1 to about 200 phr of bio-oil produced by arecombinant cell into at least one rubber including at least one dienemonomer-containing polymer or copolymer, 5 to 200 phr of at least onereinforcing filler, and a cure package, wherein the at least onereinforcing filler comprises at least one of carbon black and silica andthe amount of carbon black is no more than 30% by weight of the totalamount of reinforcing filler.
 11. The rubber method of claim 10, whereinthe recombinant cell comprises an algal cell.
 12. The method of claim10, wherein the bio-oil is present in an amount of 5 to 100 phr.
 13. Themethod of claim 10, wherein the bio-oil is present in an amount of 1 to50 phr.
 14. The method of claim 10, wherein the at least one rubbercomprises a majority by weight of at least one of polybutadiene,styrene-butadiene copolymer, natural rubber, and polyisoprene.
 15. Themethod of claim 10, wherein the oil produced by a recombinant cellcomprises at least 90% by weight of one or more fatty acids.
 16. Themethod of claim 10, wherein the oil produced by a recombinant cell haseither: at least 50% of its carbon content as naphthenic carbons, or atleast 50% of its carbon content as paraffinic carbons.
 17. A method forcontrolling the variability of fatty acid content in abio-oil-containing rubber composition, comprising incorporating about 1to about 100 phr of bio-oil produced by a recombinant cell with at leastone rubber including at least one diene monomer-containing polymer orcopolymer, 5 to 200 phr of at least one reinforcing filler, and a curepackage, thereby forming a bio-oil-containing rubber composition. 18.The method of claim 17, wherein the recombinant cell comprises an algalcell.
 19. The method of claim 17, wherein the at least one dienemonomer-containing polymer or copolymer comprises at least one ofpolybutadiene, styrene-butadiene copolymer, natural rubber, andpolyisoprene.
 20. The method of claim 17, wherein the oil produced by arecombinant cell comprises at least 90% by weight of one or more fattyacids.